Metal-nitrogen polymer compositions comprising organic electrophiles

ABSTRACT

The compositions of this invention comprise uncrosslinked reaction mixtures comprising (1) at least one organic monomer, oligomer or polymer comprising a multiplicity of organic, electrophilic substituents, and (2) at least one metal-containing polymer comprising a metal-nitrogen polymer. 
     Preferred compositions of this invention comprise reaction mixtures comprising (1) at least one organic monomer, oligomer or polymer comprising a multiplicity of organic, electrophilic substituents, and (2) at least one of: silicon-nitrogen polymers, aluminum-nitrogen polymers and boron-nitrogen and polymer combinations thereof comprising a multiplicity of sequentially bonded repeat units the compositions comprising the reaction products of the reaction mixtures, and the compositions obtained by crosslinking the reaction products of the reaction mixtures. The crosslinking may be effected through at least one of thermal-based, radiation-based free radical-based or ionic-based crosslinking mechanisms. Furthermore, the reaction mixtures, the composition comprising the reaction products and the crosslinked composition may further comprise at least one filler or reinforcement. The composition may be molded or shaped by various techniques into numerous useful articles. Furthermore, the compositions may be applied as coatings by various techniques onto numerous articles to enhance the articles usefulness.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation of application Ser. No. 08/223,294 filed on Apr.5, 1994, which is a CIP of U.S. Ser. No. 08/148,044, filed Nov. 5, 1993,abn.

BACKGROUND OF THE INVENTION

Metal-containing polymers have been used extensively in the past toprepare ceramic objects due to the high ceramic "char" yields whichresult when such polymers are heated to temperatures approaching 1000°C. Such polymers have thus proven useful when used as ceramic powderbinders, as precursors to ceramic coatings, as ceramic fiber precursors,and as powder carriers for molding applications. However, despite thehigh thermal stability of such polymers, and their ability to formceramic compositions upon thermal decomposition, the mechanical strengthof such polymers has limited their utility in applications whichrequire, for example, mechanical strength at temperatures below whichconversion to a ceramic occurs.

In contrast, while organic polymers demonstrate marginal hightemperature performance, their strength and durability at temperaturesbelow their decomposition temperature have resulted in widespreadapplication where materials such as metals or wood had previously beenused.

Block copolymers have been prepared from a variety of organic polymersystems. In addition, block copolymers have been prepared from a varietyof inorganic polymer systems. For example, U.S. Pat. 5,229,468, entitled"Polymer Precursor for Silicon Carbide/Aluminum Nitride Ceramics" whichissued in the name of Jensen on Jul. 20, 1993, discloses recent workrelating to novel block copolymers which are ceramic precursors andwhich incorporate, alternately, a multiplicity of units comprising Al--Nbond ed segments with a multiplicity of units comprising Si--N bondedsegments.

Such block copolymers, whether wholly organic in nature or whollyinorganic in nature, have been shown to exhibit certain desirablecharacteristics inherent in each of their component compositions.

Recently there has also been some effort in preparing mixedorganic/inorganic polymer compositions by, for example, the hydrolysisof Si(OR)₄ compounds in which R is an unsaturated, polymerizable organicgroup such as vinyl or allyl, or an acrylate or methacrylate-basedgroup. Efforts in preparing mixed organic/inorganic polymer compositionshave been motivated by limitations which derive from the insolubility ofmany important engineering polymers within sol-gel solutions.Free-radical curing of such "sol-gel" processed monomers results inmixed systems demonstrating some of the useful properties of the organiccomponents used in the synthesis of the monomers as well as some of thedesirable properties of the inorganic components. Typically, suchsystems comprise semi-interpenetrating networks composed of linearorganic polymers and a three-dimensional SiO₂ network. Representative ofsuch an approach is work described by B. M. Novak and C. Davies inMacromolecules, 1991, 24, 5481-5483.

Other work (see, for example, U.S. Pat. No. 4,448,939, entitled"Polyurethanes Prepared Using Poly(Silyldiamines)"), which issued in thenames of Fasolka et al., on May 15, 1984), is based on the reaction of--Si--NH--R-- (silyl amine) groups with organic isocyanates. In thiswork, polyurethane compositions comprising the reaction product of anorganic polyisocyanate and a poly(silyldiamine) are described. As shownlater herein, these compositions differ from the concepts taught in thepresent invention.

Similar work by A. A. Zhdanov et. al. in Polymer Science U.S.S.R., Vol.23, No. 11, pp 2687-2696 (1981), describes the reaction of anitrogen-hydrogen bond, present in the silyl amine end groups of linearpolysilazasiloxanes, with carbonate moieties in mixed polycarbonatesilazasiloxane compositions. Such silyl amine end groups are formed bythe reaction of hydroxyl groups in the organic fraction of thecomposition with cyclosilazane rings, resulting in ring opening andconcurrent formation of the reactive Si--NH₂ moiety.

U.S. Pat. No. 4,929,704 entitled "Isocyanate- and Isothiocyante-ModifiedPolysilazane Ceramic Precursors", which issued in the name of Schwark,on May 29, 1990; U.S. Pat. No. 5,001,090 entitled "Silicon NitrideCeramics from Isocyanate- and Isothiocyante-Modified Polysilazanes",which issued in the name of Schwark, on Mar. 19, 1991; and U.S. Pat. No.5,021,533 entitled "Crosslinkable Poly(thio)ureasilazane CompositionContaining a Free Radical Generator", which issued in the name ofSchwark, on Jun. 4, 1991, all disclose the preparation of partiallycrosslinked organic isocyanate-modified silazane polymers by the initialreaction of less than about 30 weight percent of an organic isocyanatewith a polysilazane comprising Si--H bonds so as to effect reaction ofthe isocyanate with the silicon-nitrogen bond followed by a crosslinkingreaction in which a by-product is hydrogen gas. Similarly, U.S. Pat. No.5,032,649 entitled "Organic Amide-Modified Polysilazane CeramicPrecursors", which issued in the name of Schwark, on Jul. 16, 1991, andU.S. Pat. No. 5,155,181 entitled "(Thio)amide-Modified Silazane PolymerComposition Containing a Free Radical Generator", which issued in thename of Schwark, on Oct. 13, 1992, both disclose the preparation oforganic amide-modified silazane polymers by the initial reaction of, forexample, less than about 30 wt % of an organic amide with a polysilazanecomprising Si--H bonds so as to effect reaction of the isocyanate withthe silicon-nitrogen bond followed by a crosslinking reaction in which aby-product is hydrogen gas.

U.S. Pat. No. 3,239,489, entitled "Polyurea-silazanes and Process ofPreparation", which issued in the names of Fink et al., on Mar. 8, 1966,describes the one-step preparation of linear as well as crosslinkedpolymers by the reaction of certain silazanes comprising no nitrogen tocarbon bonds within the repeat units of the silazane with di- orpoly-functional isocyanates. By reacting such compositions, both linearand crosslinked polymers can be prepared by reacting the di- orpoly-functional isocyanates with the N--H bond of the silazane.

To date, no art has disclosed or recognized the importance of: (1) thesynthesis of uncrosslinked, but crosslinkable inorganic/organic hybridpolymers or ceramers by the reaction of at least one organicelectrophile with at least one metal-nitrogen polymer (e.g.,polysilazane, polyalazane, polyborazine, poly(silazane/alazane), etc.);(2) suitable crosslink mechanisms for such polymers in a secondprocessing step; or (3) the crosslinked compositions obtained therefrom.For other silicon-nitrogen based polymers, as well as metal-nitrogenpolymers in general, for example, aluminum-nitrogen polymers,boron-nitrogen polymers, and copolymers and terpolymers prepared from,for example, aluminum-nitrogen/boron-nitrogen copolymers, andsilicon-nitrogen/boron-nitrogen copolymers, no systems are known.

Furthermore, the utility of such inorganic/organic hybrid polymers orceramers in applications not involving a pyrolysis conversion to aceramic material has never been contemplated.

The art is replete with examples of organic polymers utilized for manydifferent traditional applications. However, a need exists to expand theuse of polymers or polymer-like materials into some non-traditionalareas.

For example, much effort has been focused on enhancing the elevatedtemperature properties of organic polymers to permit such polymers tofunction effectively in various high temperature environments. However,the elevated temperature performance of organic polymers is limited bythe tendency of organic polymers to degrade and/or decompose intounacceptable or undesirable elements.

Moreover, certain uses of organic polymers are not practical becausesuch polymers typically lack flame retardant properties and in someinstances even function as fuel to sustain combustion. Accordingly, theuse of combustible polymers for many applications may not be acceptableor permissible.

Further, many organic polymers exhibit unacceptable degradation whenexposed to ultraviolet ("UV") radiation. The inherent susceptibility ofsuch polymers to UV radiation is caused by the bonds in the polymerbreaking because UV radiation possesses energy levels corresponding tosome of the bond energies within the polymers. The correspondence of thebond energies to UV radiation causes organic polymers to degrade via,for example, a bond scission mechanism. Efforts to reduce thesusceptibility of organic polymers to UV radiation has included, forexample, the incorporation of expensive ingredients that attempt toabsorb harmful UV radiation. The cost for incorporating theseingredients can be prohibitive.

Further, many organic polymers have been excluded from certainapplications where the polymers lack adhesive properties, even thoughcertain other properties of the polymers may be desirable. Some of theapplications which require polymers to exhibit certain desirableadhesive properties include those applications where a polymer is placedas a coating upon a substrate material. If the polymer lacks adhesiveproperties, the polymer coating may flake or spall from the substratematerial. Additionally, in certain situations it may be desirable toform a composite material from a polymer and another reinforcingmaterial. In this case, it is desirable for the polymer to bond oradhere to the reinforcing phase in order to form a desirable polymermatrix composite material.

Accordingly, for these and other reasons, organic polymers have beenrelegated to applications which do not expose the polymers to theirweakness. Thus, the inherent weaknesses exhibited by polymers has keptpolymers from realizing even broader applications.

The art also contains certain examples of inorganic polymers, with anemphasis in the art being placed on certain preceramic polymers. Theseinorganic polymers have been developed primarily with an emphasis ontheir char or conversion yield. Specifically, a high char yield has beena primary goal of this type of polymer because the conversion of polymerto ceramic needed to be maximized. This emphasis on optimum conversionhas resulted in the use of these preceramic polymers as precursors toceramic. Additionally, any practical use of the preceramic polymers aspolymers, per se, has been discouraged because of their relatively poormechanical properties exhibited by preceramic polymers. Moreover, somepreceramic polymers require stringent storage conditions. For example,some inorganic preceramic polymers require refrigeration to suppressreactions that would otherwise occur spontaneously at room temperatureor even below room temperature. Further, processing of some inorganicpreceramic polymers is complicated by their viscous character. In turn,this viscous character typically requires expensive pressure processingequipment. Accordingly, due to the aforementioned considerations, theuse of perceramic polymers for anything other than precursors to ceramicmaterials has not been considered and/or has been impractical.

The present invention capitalizes on foresight and the understanding ofthe limitations exhibited by wholly organic or wholly inorganicpolymers. To this end, the present invention recognizes the inherentlimitations exhibited by each class of organic and inorganic polymers.However, it has been unexpectedly discovered that certain synergisticeffects can be realized by combining organic and inorganic polymers in anovel manner to achieve a new class of materials--hybrid polymers orceramers.

Accordingly, the present invention satisfies a long felt need byovercoming the above-discussed limitations associated with whollyorganic polymers by combining synergistically organic polymers andinorganic polymers. Specifically, the present invention results in,among other things, polymers which have elevated temperatureapplicability; polymers which adhere to various surfaces, especially toinorganic surfaces, heretofore uncharacteristic of organic polymers(e.g., not only do the hybrid polymers or ceramers provide excellentmatrices for reinforced composites, but the hybrid polymers or ceramersfacilitate the joining of any type and/or number of materials to allowthe combination of materials heretofore considered difficult, if notimpossible, to join); polymers which exhibit superior UV radiationresistance; and polymers which exhibit flame retardant characteristics.

Further, the present invention satisfies a long felt need for materialspossessing characteristics of inorganic polymers combined with simpleprocessing. The present invention satisfies this need by providinghybrid polymers or ceramers from mixtures including, for example, lowviscosity liquids that are inexpensively processed into the most complexof shapes and then transformed into solids. For these and many unstatedreasons, the novel compositions of the invention, and materials derivedtherefrom, satisfy a long felt need for a new class of materialsapplicable in ways that transcend traditional notions applicable toeither wholly organic and/or wholly inorganic polymers.

SUMMARY OF THE INVENTION

Briefly, the present invention relates to novel mixtures and the novelcompositions derived from the mixtures. The novel mixtures comprise atleast one organic electrophile and at least one metal-containingpolymer. The at least one organic electrophile comprises at least onemonomer, oligomer or polymer, and more particularly, the at least oneorganic monomer, oligomer or polymer comprising a plurality of organic,electrophilic constituents. The metal-containing polymer comprises atleast one monomer, oligomer or polymer, and more particularly, at leastone metal-nitrogen polymer comprising at least one monomer, oligomer orpolymer, where the metal comprises at least one metal comprising IUPAC(International Union of Pure and Applied Chemistry) Groups 1 through 12metals, the lanthanide series metals, and metals and metalloids of IUPACGroups 13 and 14, including boron. For the purposes of the presentinvention the term metal-containing polymer is intended to include, forexample, aluminum, silicon, and boron containing polymers.

The novel compositions of the present invention are derived from thenovel mixtures and comprise hybrid polymer or ceramer compositions. Thecompositions may be uncrosslinked, partially crosslinked, substantiallycrosslinked or substantially completely crosslinked.

Moreover, the novel compositions may further comprise at least onefiller or reinforcement. The filler-containing compositions are derivedfrom novel mixtures of the present invention that are induced to atleast partially embed or surround at least one filler or reinforcement.As with the unfilled or unreinforced compositions, the at leastpartially filled or reinforced hybrid polymer or ceramer compositions ofthe present invention may be uncrosslinked, partially crosslinked,substantially crosslinked or substantially completely crosslinked.

The present invention further relates to novel mixtures and the novel,unfilled or filled, compositions derived from the mixtures. The mixturescomprise (1) at least one organic electrophile comprising at least oneorganic monomer, oligomer, or polymer comprising a plurality of organic,electrophilic substituents, and (2) at least one metal-nitrogen monomer,oligomer or polymer. Moreover, the novel, unfilled or filled, hybridpolymer or ceramer compositions may be uncrosslinked, partiallycrosslinked, substantially crosslinked or substantially completelycrosslinked.

In a preferred embodiment of the present invention, novel mixturescomprise, and novel compositions are derived from, (1) at least oneorganic electrophile comprising at least one monomer, oligomer orpolymer comprising a plurality of organic, electrophilic substituentsand (2) at least one metal-containing polymer comprising at least onemetal-nitrogen polymer comprising at least one metal of IUPAC Groups 1through 12 metals, the lanthanide series metals and metals andmetalloids of IUPAC Groups 13 and 14, including boron. Preferably, theat least one metal of the at least one metal-nitrogen polymer comprisesat least one of IUPAC Group 2 through 4 metals, the lanthanide seriesmetals, and metals and metalloids of IUPAC Groups 13 and 14, includingboron. More preferably, the at least one metal of the at least onemetal-nitrogen polymer comprises at least one of the metal andmetalloids of IUPAC Groups 13 and 14, including boron. The novel hybridpolymer or ceramer compositions derived from novel mixtures may beunfilled or filled and/or may be uncrosslinked, partially crosslinked,substantially crosslinked or substantially completely crosslinked.

In an even more preferred embodiment of the present invention, novelmixtures comprise and novel compositions are derived from, reactionmixtures comprising (1) at least one organic electrophile comprising atleast one organic monomer, oligomer, or polymer comprising a pluralityof organic, electrophilic substituents, and (2) at least onemetal-containing polymer comprising at least one of: (i) at least onemetal-nitrogen polymer comprising at least one of silicon-nitrogenpolymers, aluminum-nitrogen polymers, and boron-nitrogen polymerscomprising a plurality of sequentially bonded repeat units of the form(a), (b), (c), and (d), recited below: ##STR1## respectively, where R,R', R", and R'"=hydrogen, alkyl, alkenyl, alkynyl or aryl and A═O or S;(ii) mixtures of two or more metal-nitrogen polymers comprising two ormore of the structural units (a), (b), (c), and (d); (iii)metal-crosslinked metal-nitrogen polymers comprising one or more of thestructural units (a), (b), (c), and (d); and (iv) metal-nitrogencopolymers comprising two or more of the structural units (b), (c), and(d). These reaction mixtures react to form novel, uncrosslinked hybridpolymer or ceramer compositions which incorporate at least one organicelectrophile comprising the at least one organic monomer, oligomer, orpolymer into the structure of the one or more metal-containing polymersand which, in a subsequent step, may be crosslinked. In a furtherpreferred embodiment, an uncrosslinked liquid hybrid polymer or ceramerreaction product of the at least one organic electrophile and the one ormore metal-containing polymers comprises a liquid which may be cured toa rigid solid by crosslinking after processing the liquid into a desiredshape. The cure may be accomplished by effecting crosslinking byproviding an energy input using at least one activation meanscomprising, for example, thermal activation or radiation inducedactivation, to effect crosslinking through an ionic or radical-basedcrosslinking mechanism.

In a further preferred embodiment, the hybrid polymer or ceramerreaction products comprise sites of organounsaturation such as alkenylor alkynyl groups. Thus, when R =alkenyl or alkynyl groups, thesereaction product compositions may then be crosslinked by supplying anenergy input in the form of, for example, thermal energy or radiation,such as ultraviolet radiation, microwave radiation or electron beamradiation, to crosslink, to a desirable extent, the hybrid polymer orceramer compositions. In this case, crosslinking occurs by activatingalkenyl-based or alkynyl-based polymerization of the alkenyl or alkynylgroups within these compositions. When the reaction product comprises aliquid, such crosslinking provides a mechanism for curing the liquid toa rigid solid, if desired, after processing the liquid into a desiredshape.

The at least one organic electrophile comprising organic monomers,oligomers, or polymers comprising a plurality of electrophilicsubstituents suitable for the practice of this invention may be definedas organic monomers, oligomers or polymers which contain a plurality ofone or more reactive groups which may attack the electron density of themetal-nitrogen bond (e.g., Si--N bonds, Al--N bond s, B--N bonds, etc.)of the metal-containing polymer, resulting in the breaking of thesebonds and, subsequently, the formation of new bonds. Alternatively, whenR'=H, the at least one organic electrophile comprising organic monomers,oligomers, or polymers may preferentially, but not exclusively, react atthe N--H bonds of the metal-containing polymer. Either mechanismprovides for the incorporation of the at least one organic electrophilecomprising at least one organic monomer, oligomer or polymer into thestructure of the metal-containing polymers. In a preferred embodiment ofthe invention, such organic electrophiles comprise liquids to increasethe probability for reaction of the at least one organic electrophilecomprising at least one organic monomer, oligomer or polymer with theone or more metal-containing polymers.

Typical examples of electrophilic groups which are suitableelectrophilic substituents for the multifunctional electrophile includegroups containing, for example, the following bonding schemes: ##STR2##

Typical examples of the at least one organic electrophile comprisingorganic monomers, oligomers or polymers suitable for the practice ofthis invention include, for example, multifunctional organicisocyanates, multifunctional compounds comprising amide linkages such aspolyamides, multifunctional compounds comprising imide linkages such aspolyimides, multifunctional epoxides, multifunctional compoundscomprising ester linkages, such as polyacrylates, polycarbonates,polyvinylacetates, or polyesters, or multifunctional esters such asdimethyl adiptate, quinones (which can undergo sequential 1,4 additionreactions) and multifunctional organic acids such as polyacrylic acid.

While a wide variety of such hybrid polymers or ceramers are possible,in a preferred embodiment of the present invention those derived frommetal-nitrogen polymers, for example, silicon-nitrogen polymers,aluminum-nitrogen polymers, or boron-nitrogen polymers comprising aplurality of sequentially bonded repeat units of the form (a), (b), (c),and (d), recited below: ##STR3## where R, R', R", and R'"=hydrogen,alkyl, alkenyl, alkynyl or aryl and A=O or S, have demonstratedremarkable high temperature as well as ambient temperature performancecharacteristics. In a preferred embodiment of the present invention,liquid metal-containing polymers containing the units (a), (b), (c), and(d) above and wherein R=alkenyl or alkynyl are particularlyadvantageous, due to their tendency to generate liquid reaction productswith the organic electrophiles and their ability to then generate rigid,crosslinked structures through metal-alkenyl or metal-alkynyl groupcrosslinking after the reaction product has been shaped by a formingprocess such as suitable molding technologies. Alternatively, in anotherpreferred embodiment of the present invention, hybrid polymer or ceramercompositions may be heated to temperatures at which thermally-inducedcondensation crosslinking occurs (for example, in polyureasilazanescomprising Si--H bonds condensation crosslinking may occur with theevolution of hydrogen gas) or by providing to the hybrid polymers orceramers groups which enable chemical crosslinking through an ionicmechanism.

Such hybrid polymers or ceramers may be prepared by reactingmetal-containing polymers with at least one organic electrophilecomprising at least one organic monomer, oligomer, or polymer comprisinga plurality of organic, electrophilic substituents to prepare anuncrosslinked composition which may then be crosslinked in a subsequentprocessing step. In a preferred embodiment, the at least one organicelectrophile comprising at least one organic monomer, oligomer, orpolymer comprising a multiplicity of organic, electrophilic substituentscomprises a liquid.

Furthermore, in a preferred embodiment of the present invention, thereaction product of the at least one organic electrophile with ametal-containing polymer comprises a liquid which may be cured to arigid solid, if desired, after processing the liquid into a desiredshape. The curing may be accomplished by providing an energy input usingat least one activation means comprising thermal activation or radiationinduced activation to effect crosslinking through an ionic or radicalcrosslinking mechanism. In a further preferred embodiment, it isespecially advantageous when the reaction product of the at least oneorganic electrophile and the at least one metal-containing polymercomprises sites of organounsaturation such as alkenyl or alkynyl groups.In a subsequent step, alkenyl-based or alkynyl-based crosslinking in thereaction product may be effected by providing an energy input in theform of, for example, heat or irradiation which may be used to providethe mechanism for curing the liquid reaction product to a rigid solidafter processing the liquid into a desired shape. More preferredcompositions wherein R=alkenyl and more preferably wherein the alkenylgroup comprises vinyl may additionally comprise a free radicalinitiator, such as, for example, a peroxide or azo compound which maypromote alkenyl crosslinking in the reaction product at relatively lowtemperatures. In another preferred embodiment, compositions whereinR=alkenyl and more preferably wherein the alkenyl group comprises allylmay additionally comprise a UV initiator or sensitizer which promotescrosslinking upon UV irradiation. Suitable metal-containing polymers mayalso include: at least one mixture of two or more metal-nitrogenpolymers comprising two or more of the structural units (a), (b), (c),and (d); at least one metal-crosslinked metal-nitrogen polymercomprising one or more of the structural units (a), (b), (c), and (d);and at least one metal-nitrogen copolymer comprising two or more of thestructural units (a), (b), (c), and (d).

Representative of metal-containing polymers comprising the repeat units(a) comprise those polymers disclosed in, for example, U.S. Pat. No.4,929,704 entitled "Isocyanate- and Isothiocyante-Modified PolysilazaneCeramic Precursors", which issued in the name of Schwark, on May 29,1990; U.S. Pat. No. 5,001,090 entitled "Silicon Nitride Ceramics fromIsocyanate- and Isothiocyante-Modified Polysilazanes" which issued inthe name of Schwark, on Mar. 19, 1991; and U.S. Pat. No. 5,021,533entitled "Crosslinkable Poly(thio)ureasilazane Composition Containing aFree Radical Generator", which issued in the name of Schwark, on Jun. 4,1991; and polymers described in references contained in these U.S.Patents. The entire disclosures of these U.S. Patents are specificallyincorporated herein by reference.

Representative of metal-containing polymers comprising the repeat units(b) comprise those polymers described in, for example, U.S. Pat. No.3,505,246 entitled "Nitrogen Aluminum Hydride Polymers and Methods ofMaking the Same", which issued in the names of Ehrlich et al., on Apr.7, 1970; U.S. Pat. No. 4,687,657 entitled "Fabrication of SiC--AlNAlloy", which issued in the names of Clark et al., on Aug. 18, 1987;U.S. Pat. No. 4,696,968 entitled "Melt-Formable Organoaluminum Polymer",which issued in the name of Tebbe, on Sep. 29, 1987, and U.S. Pat. No.5,276,105, entitled "Polymer Precursors for Aluminum Nitride", whichissued in the name of Jensen, on Jan. 4, 1994; and polymers described inreferences contained in these U.S. Patents. The entire disclosures ofthese U.S. Patents are specifically incorporated herein by reference.

Representative of metal-containing polymers comprising the repeat units(c) comprise those polymers described in, for example, U.S. Pat. No.4,707,556 entitled "Boron Nitride Polymeric Precursors", which issued inthe names of Paciorek et al., on Nov. 17, 1987; U.S. Pat. No. 4,581,468entitled "Boron Nitride Preceramic Polymers", which issued in the namesof Paciorek et al., on Apr. 8, 1986; U.S. Pat. No. 3,288,726 entitled"B--N Linked Borazane Derivatives and Their Preparation", which issuedin the name of Wagner, on Nov. 29, 1966; and in the article by R. T.Paine and C. K. Narula, Chem. Rev., 90 (1990) 73-91 and polymersdescribed in references contained therein. The entire disclosures ofthese U.S. Patents and the article are specifically incorporated hereinby reference.

Representative of metal-containing polymers comprising the repeat units(d) comprise those polymers described, for example, in U.S. Pat. No.4,482,669 entitled "Preceramic Organosilazane Polymers", which issued inthe names of Seyferth et al., on Nov. 13, 1984; U.S. Pat. No. 4,774,312entitled "Polydisilacyclobutasilazanes", which issued in the name ofBurns, on Sep. 27, 1988; U.S. Pat. No. 4,689,252 entitled "PolysilazaneComposition which can Crosslink in the Presence of a Metal CompoundCatalyzing a Hydrosilylation Reaction", which issued in the names ofLebrun et al., on Aug. 25, 1987; U.S. Pat. No. 4,612,383 entitled"Method of Producing Polysilazanes", which issued in the names of Laineet al., on Sep. 16, 1986; U.S. Pat. No. 4,675,424 entitled "Method ofMaking Polysilazanes", which issued in the names of King, III, et al.,on Jun. 23, 1987; U.S. Pat. No. 4,722,988 entitled "OrganopolysilazaneComposition Containing Free Radical Generators and Capable of BeingCrosslinked by an Energy Input", which issued in the names of Porte etal., on Feb. 2, 1988; U.S. Pat. No. 5,155,181 entitled"(Thio)amide-Modified Silazane Polymer Composition Containing a FreeRadical Generator", which issued in the name of Schwark, on Oct. 13,1992; U.S. Pat. No. 5,032,649 entitled "Organic Amide-ModifiedPolysilazane Ceramic Precursors", which issued in the name of Schwark,on Jul. 16, 1991; U.S. Pat. No. 4,929,704 entitled "Isocyanate- andIsothiocyante-Modified Polysilazane Ceramic Precursors", which issued inthe name of Schwark, on May 29, 1990; U.S. Pat. No. 5,001,090 entitled"Silicon Nitride Ceramics from Isocyanate- and Isothiocyante-ModifiedPolysilazanes", which issued in the name of Schwark, on Mar. 19, 1991;U.S. Pat. No. 5,021,533 entitled "Crosslinkable Poly(thio)ureasilazaneComposition Containing a Free Radical Generator", which issued in thename of Schwark, on Jun. 4, 1991; U.S. Pat. No. 3,853,567 entitled"Production of Shaped Articles of Homogeneous Mixtures of SiliconCarbide and Nitride", which issued in the name of Verbeck, on Dec. 10,1974, and polymers described in references contained therein. The entiredisclosures of these U.S. Patents are specifically incorporated hereinby reference.

Representative of metal-containing polymer mixtures of polymerscomprising the structural units (b) and (c) comprise those polymersdescribed, for example, in U.S. Pat. No. 4,764,489 entitled "Preparationof Mixed Boron and Aluminum Nitrides", which issued in the name of Bolt,on Aug. 16, 1988, and polymers described in references containedtherein. The entire disclosure of U.S. Pat. No. 4,764,489 isspecifically incorporated herein by reference.

Representative of polymer mixtures of metal-containing polymerscomprising the structural units (b) and (d) comprise those polymersdisclosed in, for example, U.S. Pat. No. 5,229,468, entitled "PolymerPrecursor for Silicon Carbide/Aluminum Nitride Ceramics", which issuedin name of Jensen, on Jul. 20, 1993, and polymers described inreferences contained therein. The entire disclosure of U.S. Pat. No.5,229,468 is specifically incorporated herein by reference.

Representative of polymer mixtures of metal-containing polymerscomprising the structural units (c) and (d) comprise those polymersdescribed, for example, in U.S. Pat. No. 5,164,344 entitled"Borosilazanes as Binders for the Preparation of Sintered SiliconCarbide Monoliths", which issued in the name of Zank, on Nov. 17, 1992,and polymers described in references contained therein. The entiredisclosures of U.S. Pat. No. 5,164,344 is specifically incorporatedherein by reference.

Important applications include the use as coatings or molding of thesepolymeric materials, with or without the inclusion of fillers orreinforcements to achieve hybrid polymer or ceramer coatings onsubstrate materials or molded the unfilled or filled polymers shapedinto a desired object. Such polymeric materials are, in themselves,desirable because they possess a variety of characteristics otherwiseunobtainable using conventional materials. Often such objects may beheat-treated to temperatures below their pyrolysis temperatures (e.g. totemperatures within the range of about 25° C. to about 500° C.) toachieve a desirable crosslink density without conversion to a ceramicmaterial. Such processing is often desirable when a coating or moldedobject comprising such hybrid polymer or ceramer materials is exposed totemperatures within this range during its use. While themetal-containing polymers suitable for the practice of this inventionmay comprise any metal, in a preferred embodiment of the presentinvention compositions comprise metal-nitrogen polymers containing, forexample, the metals silicon, aluminum, boron and combinations thereof.Crosslinking may be effected by providing an energy input using variousactivation means including, for example, thermal activation or radiationinduced activation to effect crosslinking through an ionic orradical-based mechanism.

It has been unexpectedly discovered that crosslinked, covalently-bondedcopolymers comprising: (1) organic segments derived from organicelectrophiles, and (2) inorganic fractions derived from segments ofmetal-nitrogen polymers, demonstrate various desirable synergisticcombinations of properties. For example, these copolymers exhibit thehigh mechanical strengths of their wholly organic counterparts atambient temperature, as well as the extended high temperatureperformance of their wholly inorganic counterparts. Such combinations ofproperties overcome many of the limitations encountered in whollyorganic or wholly inorganic polymers.

Moreover, it has also been discovered that such crosslinked,covalently-bonded hybrid copolymers or ceramers exhibit certaindesirable characteristics (such as, for example, extended thermalstability and high thermal char relative to their wholly organiccounterparts) when used in high temperature applications or applicationswhere char-forming behavior is important. With regard to char formation,it is well known that char-forming materials such as phosphates are usedas additives to organic polymers as flame retardants. The hybrid polymeror ceramer compositions of the present invention which exhibit high charyields are thus flame retardant compositions.

Moreover, it has also been unexpectedly discovered thatcovalently-bonded hybrid polymers or ceramers exhibit certain desirablecharacteristics (such as, for example, weatherability or UV lightresistance relative to their wholly organic counterparts) when used inoutdoor applications as, for example, molded objects or coatings.

Moreover, it has also been unexpectedly discovered that the covalentlybonded hybrid polymers or ceramers exhibit certain desirablecharacteristics (such as, for example, adhesion to, for example, metals,organic polymers, inorganic polymers, ceramics, metal matrix composites,polymer matrix composites, ceramic matrix composites, natural materials,etc., relative to their wholly organic or wholly inorganic counterparts)when used in, for example, the joining of similar or dissimilarmaterials or the formation of filled or reinforced hybrid or ceramermatrix composites.

Moreover, it has also been unexpectedly discovered that certaincovalently-bonded hybrid polymers or ceramers exhibit certain desirablecharacteristics (such as, for example, superior non-frictionalproperties or non-stick properties relative to their wholly organiccounterparts) when used in, for example, cookware applications or roomtemperature or high temperature mechanical equipment or chemicalprocessing equipment.

Moreover, it has also been unexpectedly discovered that certain of thecovalently bonded hybrid polymers or ceramers exhibit certain desirablecharacteristics (such as, for example, wear resistance or abrasionresistance relative to their wholly organic counterparts) when used ascoatings at room temperature and elevated temperatures.

Moreover, it has also been unexpectedly discovered that certain of thecovalently bonded hybrid polymers or ceramers exhibit certain desirablecharacteristics (such as, for example, transparency and dimensionalstability relative to their wholly organic counterparts) when used at,for example, elevated temperatures as transparent objects.

It is expected that any number of combinations of properties of thehybrid polymers or ceramers may be tailored to exhibit more desirableroom temperature and/or high temperature characteristics relative totheir wholly organic and/or wholly inorganic parts. Thesecharacteristics include, for example, transparency and/or rigidity orstiffness and/or abrasion resistance and/or weatherability or UV lightresistance and/or permeability and/or water repellency and/or fatigueresistance and/or creep resistance and/or frictional properties and/orwear resistance and/or flame resistance and/or temperature resistanceand/or electrical insulating properties (e.g., dielectric properties)and/or low moisture absorption (e.g., water, steam, etc.) and/orcoefficient of thermal expansion and/or thermal conductivity and/orradiation resistance and/or dimensional stability and/or dimensionaltolerance stability and/or adhesion and/or dissipation factor and/orcorrosion resistance and/or erosion resistance, etc.

The unexpected superior properties of the polymers of the presentinvention, that is, the hybrid polymers or ceramers of the presentinvention result from the synergism of the organic and inorganiccomponents disclosed above herein.

Definitions

"Copolymer", as used herein, means a polymer made from two or moremonomers, oligomers or polymers corresponding to different repeat units,where the different repeat units are incorporated in the same polymericmolecule or chain. Copolymers include random copolymers, di-blockcopolymers, multiblock copolymers, alternating copolymers, graftcopolymers, organic copolymers, inorganic copolymers, hybrid copolymers(e.g., both organic and inorganic backbone copolymers), organic graftcopolymers, inorganic graft copolymers, hybrid graft copolymers bothorganic and inorganic grafts on the same copolymer), terpolymers, etc.

"Organic Electrophile", as used herein, means at least one organicmonomer, oligomer or polymer comprising a plurality of electrophilicsubstituents wherein each of the at least one organic monomer, oligomeror polymer contains a plurality of one or more electrophilic, reactivegroups which may attack the electron density of a metal-containingpolymer and in a preferred embodiment a metal-nitrogen bond (e.g., Si--Nbonds, Al--N bonds, B--N bonds, etc.) of the metal-containing polymerresulting in the breaking of these bonds and, subsequently, theformation of new bonds. Alternatively, when the metal-containing polymercomprises a metal-nitrogen polymers comprising side groups comprisinghydrogen bonded to nitrogen, the at least one electrophilic organiccomprising organic monomer, oligomer or polymer may preferentially reactat the N--H bonds of the metal-containing polymer. Examples ofelectrophilic groups which are suitable electrophilic substituents forthe multifunctional electrophile include groups containing, for example,the following bonding schemes: ##STR4## and the like.

Examples of organic electrophiles comprising organic monomers, oligomersor polymers suitable for the practice of the present invention include,for example, multifunctional organic isocyanates, multifunctionalcompounds comprising amide linkages (such as polyamides),multifunctional compounds comprising imide linkages (such aspolyimides), multifunctional epoxides, multifunctional compoundscomprising ester linkages (such as polyacrylates, polycarbonates,polyvinyl acetates, polyesters, etc.), or multifunctional esters (suchas dimethyladipate), quinones (which undergo sequential 1,4 additionreactions) and multifunctional organic acids such as polyacrylic acid.

"Filler" or "Reinforcement", as used herein, is intended to includeeither single constituents or mixtures of constituents which are eitherchemically reactive and/or which are substantially unaffected by and/orof limited solubility in the polymer matrix and may be single ormultiple phase. Fillers may be provided in a wide variety of forms andsizes, such as powders, flakes, platelets, microspheres (both hollow andsolid), whiskers, bubbles, etc., and may be either dense or porous.Filler may also include ceramic fillers, such as alumina or siliconcarbide or boron carbide and zirconium oxide, as continuous fibers,yarns or tows, chopped fibers, particulates, whiskers, bubbles, spheres,fiber mats, three-dimensionally woven structures, or the like, mixturesthereof, and coated fillers such as ceramic coated fillers such ascarbon fibers coated with alumina or silicon carbide. Fillers may alsoinclude metal fillers, such as fibers, chopped fibers, particulates,whiskers, bubbles, spheres, fiber mats, woven three-dimensionalstructures, or the like, mixtures thereof and metal-coated fillers suchas organic or inorganic fibers coated with metal, IUPAC Groups 1 through12 metals, the lanthanide series metals and metals and metalloids ofIUPAC Groups 13 and 14, including boron and alloys and/or combinationsthereof. Furthermore, fillers may also include plastic or polymerfillers, such as olefinics, vinylics, styrenics, acrylonitrilics,acrylics, cellulosics, polyamides, polyesters, polyacarbonates, sulfonepolymers, imide polymers, ether-oxide polymers, ketone polymers,fibropolymers and combinations thereof as fibers, chopped fibers,particulates, whiskers, bubbles, spheres, fiber mats,three-dimensionally woven structures, or the like, mixtures thereof andcoated plastic or organic fillers such as nylon fibers coated with ametal and the like. Furthermore, fillers or reinforcement in aparticulate class may include, but are not limited to, minerals (e.g.,calcium carbonate, silica, kaolin, talc, alumina trihydrate, feldspar,baryte, calcium sulfate, etc.), solid or hollow glass spheres, metaloxides (e.g., oxides and mixed oxides of metals of IUPAC Groups 1through 12, the lanthanide series metals, metals and metalloids of IUPACGroups 13 and 14, including boron, etc.), metal carbides (e.g., carbidesand mixed carbides of metals of IUPAC Groups 1 through 12, thelanthanide series metals, metals and metalloids of IUPAC Groups 13 and14, including boron, etc), metal borides (e.g., boride and mixed boridesof metals of IUPAC Groups 1 through 12, the lanthanide series metals,metals and metalloids of IUPAC Groups 13 and 14, etc.), metal nitrides(e.g., nitride and mixed nitrides of metals of IUPAC Groups 1 through12, the lanthanide series metals, metals and metalloids of IUPAC Groups13 and 14, including boron, etc.), carbon black, and the like, asparticulates. Fillers or reinforcements in a fiber class include glassfibers, carbon or graphite fibers, metal fibers, asbestos, whiskers,polymeric fibers (e.g., polyamides, polyesters, alaphatic polyamides,polyethyleneterathalates, aramides, aromatic polyamides,polyetherketone, polyethylene, etc.) and ceramic fibers (e.g., NICALON™silicon carbide, etc.). Fillers or reinforcements primarily in the discor platey class include, for example, mica, glass flakes, aluminaflakes, aluminum, etc.

"Hybrid Polymer" or "Ceramer", as used herein, means an oligomer,polymer, copolymer or polymer alloy which is comprised of a plurality ofmetal-containing segments and a plurality of organic segments. Thehybrid polymer or ceramer may be at least one of copolymeric or polymeralloy. Hybrid polymers or ceramers may include random copolymers,di-block copolymers, multiblock copolymers, alternating copolymers,graft copolymers, terpolymers, etc.

"Metal-Containing Polymer", as used herein, means a metal-containingmonomer, oligomer or polymer. In a preferred embodiment, themetal-containing monomer, oligomer or polymer comprises a metal-nitrogenpolymer. Metal, when used in combination with metal-containing and inparticular with metal-nitrogen polymer means a metal from IUPAC(International Union of Pure and Applied Chemistry) Groups 1 through 12,the lanthanide series metals and metals and metalloids from IUPAC Groups13 and 14, including boron. Preferred metals comprise metals from IUPACGroups 2 through 4, the lanthanide series metals, and metals andmetalloids from IUPAC Groups 13 and 14, including boron. More preferredmetals comprise metals from metals and metalloids from IUPAC Groups 13and 14, including boron. Even more preferred metals comprise silicon,aluminum and boron.

"Metal Matrix Composite" or "MMC", as used herein, means a materialcomprising two or three-dimensionally interconnected alloy or matrixmetal which has embedded at least one reinforcing phase. The matrixmetal may include various alloying elements to provide specificallydesired mechanical and/or physical properties in the resultingcomposite.

"Metal-Nitrogen Polymer", as used herein, means monomers, oligomers orpolymers comprising repeat units wherein metal atoms are bonded to atleast one nitrogen atom. In a preferred embodiment, the metal atoms arebonded to at least two nitrogen atoms. Metal-nitrogen polymers includemetal-nitrogen monomers, oligomers or polymers, wherein the metalcomprises a metal from IUPAC (International Union of Pure and AppliedChemistry) Groups 1 through 12, the lanthanide series metals, metals andmetalloids from IUPAC Groups 13 and 14, including boron. Preferredmetals comprise metals from IUPAC Groups 2 through 4, the lanthanideseries metals, and the metals and metalloids of IUPAC Groups 13 and 14,including boron. More preferred metals comprise metals from metals andmetalloids from IUPAC Groups 13 and 14, including boron. Even morepreferred metals comprise silicon, aluminum and boron. Even morepreferred, metal-nitrogen polymers include silicon-nitrogen polymers,aluminum-nitrogen polymers, boron-nitrogen polymers, mixtures of two ormore metal-nitrogen polymers, metal-crosslinked metal-nitrogen polymersand metal-nitrogen copolymers. The metal-nitrogen polymers can be in theform of at least one of cyclic oligomers, cage compounds, ring basepolymers, linear polymers, etc.

"Mixture" or "Reaction Mixture", as used herein, means the physicalcombination of at least organic one monomer, oligomer or polymer and atleast one metal-containing monomer, oligomer or polymer.

"Monome", as used herein, means a molecule or chemical compoundcomprising one repeat unit with an inherent capability of formingchemical bonds with the same and/or other monomers oligomers or polymersin such a manner that oligomeric and/or polymeric molecules ormacromolecules are formed. Monomers include molecules or chemicalcompounds which are wholly organic, wholly inorganic or hybrid (i.e.,organic and inorganic).

"Oligomer", as used herein, means a molecule or chemical compound whichcomprises several repeat units, generally from about 2 to about 10repeat units. Oligomers have an inherent capability of forming chemicalbonds with the same and/or other monomers and/or oligomers and/orpolymers in such a manner that oligomeric and/or polymeric molecules ormacromolecules are formed including molecules or chemical compoundswhich are wholly organic, wholly inorganic, or hybrid (i.e., organic andinorganic).

"A Plurality or Multiplicity of Electrophilic Substituents", as usedherein, means at least two reactive groups within the same monomer,oligomer or polymer which cause metal-nitrogen bond (e.g., the S--N bondin a silicon-nitrogen co-reactant polymer) or nitrogen-hydrogen bond(N--H bond) scission within a metal-nitrogen co-reactant polymer.Examples of electrophilic groups which are suitable electrophilicsubstituents for the multifunctional electrophile include groupscontaining, for example, the following bonding schemes: ##STR5## and thelike.

"Polymer", as used herein, means a molecule or compound which comprisesa large number of repeat units, generally greater than about 10 repeatunits. Polymer includes thermosetting polymers, thermoplastic polymers,elastomers, amorphous polymers, crystalline polymers, semicrystallinepolymers, homopolymers, heteropolymers, copolymers, polymer alloys,linear or unbranched polymers, branched polymers such as macromoleculescomprising long branching, short branching or mixed long and shortbranching, cyclic polymers, crosslinkable polymers, crosslinkedpolymers, polymeric network polymers, interpenetrating polymericnetworks, combinations thereof, etc. Additionally, polymers includewholly organic, wholly inorganic and hybrid (i.e., organic andinorganic) chemical macromolecules.

"Preform" or "Permeable Preform, as used herein, means a porous mass ofat least one filler or reinforcement which is manufactured with at leastone surface boundary which essentially defines a boundary forinfiltrating matrix materials, such mass retaining sufficient shapeintegrity and green strength to provide dimensional fidelity prior tobeing infiltrated by the matrix. The mass should be sufficiently porousto accommodate infiltration of the matrix thereinto. A preform typicallycomprises a bounded array or arrangement of filler or reinforcement,either homogeneous or heterogeneous, and may be comprised of anysuitable material (e.g., mineral and/or ceramic and/or polymer and/ormetal and/or composite particulates, powders, fibers, whiskers, etc.),and any combination thereof). A preform may exist either singularly oras an assemblage.

"Ceramic Matrix Composite" or "CMC" or "Ceramic Composite Body", as usedherein, means a material comprising a two- or three-dimensionallyinterconnected ceramic which has embedded at least one reinforcementphase, and may further include a metal phase embedded therein; possiblyin a two- or three-dimensionally interconnected network.

"Polymer Matrix Composite" or "PMC", as used herein, means a materialcomprising a two-or three-dimensionally interconnected matrix polymerwhich has embedded at least one filler or at least one preform of atleast one filler. The matrix polymer may include various polymers toprovide specifically desired chemical, mechanical and physicalproperties in the resulting composite.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 represents a comparison of weight retained (TG, % Sample Wt.) asa function of temperature for a wholly organic epoxy resin composition(Curve A) and a hybrid or ceramer epoxy resin (about 50 wt %)composition (Curve B) comprising a silicon-nitrogen polymer coreactant(about 50 wt %) when the samples are heated to about 1000° C. in anitrogen atmosphere at about 5° C. per minute (Thermal GravimetricAnalysis technique).

FIG. 2 represents a comparison of weight retained (TG, % Sample Wt) as afunction of temperature for a wholly organic urethane resin composition(Curve C) and a hybrid or ceramer urethane resin (about 80 wt %)composition (Curve D) comprising a silicon-nitrogen polymer correctant(about 20 wt %) when the samples are heated to about 1000° C. in anitrogen atmosphere of about 5° C. per minute.

DETAILED DESCRIPTION OF THE INVENTION

Briefly, the present invention relates to novel mixtures and the novelcompositions derived from the mixtures. The novel mixtures comprise atleast one organic electrophile and at least one metal-containingpolymer. The at least one organic electrophile comprises at least onemonomer, oligomer or polymer, and more particularly, the at least oneorganic monomer, oligomer or polymer comprising a plurality of organic,electrophilic constituents. The metal-containing polymer comprises atleast one monomer, oligomer or polymer, and more particularly, at leastone metal-nitrogen polymer comprising at least one monomer, oligomer orpolymer, wherein the metal comprises at least one metal comprising IUPAC(International Union of Pure and Applied Chemistry) Groups 1 through 12metals, the lanthanide series metals, and metals and metalloids of IUPACGroups 13 and 14, including boron.

The novel compositions of the present invention are derived from thenovel mixtures and comprise hybrid polymer or ceramer compositions. Thecompositions may be uncrosslinked, partially crosslinked, substantiallycrosslinked or substantially completely crosslinked.

Moreover, the novel compositions may further comprise at least onefiller or reinforcement. The filler-containing compositions are derivedfrom novel mixtures of the present invention that are induced to atleast partially embed or surround at least one filler or reinforcement.As with the unfilled or unreinforced compositions, the at leastpartially filled or reinforced hybrid polymer or ceramer compositions ofthe present invention may be uncrosslinked, partially crosslinked,substantially crosslinked or substantially completely crosslinked.

Particularly, the present invention relates to novel mixtures and thenovel, unfilled or filled, compositions derived from the mixtures. Themixtures comprise (1) at least one organic electrophile comprising atleast one organic monomer, oligomer, or polymer comprising a pluralityof organic, electrophilic substituents, and (2) at least onemetal-nitrogen monomer, oligomer or polymer. Moreover, the novel,unfilled or filled, hybrid polymer or ceramer composition may beuncrosslinked, partially crosslinked, substantially crosslinked orsubstantially completely crosslinked.

In a preferred embodiment of the present invention, novel mixturescomprise, and novel compositions are derived from, (1) at least oneorganic, electrophile comprising at least one monomer, oligomer orpolymer comprising a plurality of organic, electrophilic substituentsand (2) at least one metal-containing polymer comprising at least onemetal-nitrogen polymer comprising at least one metal of IUPAC Groups 1through 12 metals, the lanthanide series metals and metals andmetalloids of IUPAC Groups 13 and 14, including boron. Preferably, theat least one metal of the at least one metal-nitrogen polymer compriseat least one of IUPAC Group 2 through 4 metals, the lanthanide seriesmetals, and metals and metalloids of IUPAC Groups 13 and 14, includingboron. More preferably, the at least one metal of the at least onemetal-nitrogen polymer comprises at least one of the metal andmetalloids of IUPAC Groups 13 and 14, including boron. For the purposesof the present invention the term metal-containing polymer is intendedto include, for example, aluminum, silicon, and boron containingpolymers. The novel hybrid polymer or ceramer compositions derived fromnovel mixtures may be unfilled or filled and/or may be uncrosslinked,partially crosslinked, substantially crosslinked or substantiallycompletely crosslinked.

In an even more preferred embodiment of the present invention, novelmixtures comprise, and novel compositions are derived from, reactionmixtures comprising (1) at least one organic electrophile comprising atleast one organic monomer, oligomer or polymer comprising a plurality oforganic, electrophilic substituents, and (2) at least onemetal-containing polymer comprising, for example, at least one of: (i)at least one metal-nitrogen polymer selected from the group consistingof silicon-nitrogen polymers, aluminum-nitrogen polymers andboron-nitrogen polymers comprising a multiplicity of sequentially bondedrepeat units of the form (a), (b), (c), and (d), recited below: ##STR6##respectively, where R, R', R", and R'"=hydrogen, alkyl, alkenyl, alkynylor aryl groups and A=O or S; (ii) at least one mixture of two or moremetal-nitrogen polymers comprising two or more of the structural units(a), (b), (c), and (d); (iii) at least one metal-nitrogenmetal-crosslinked polymers comprising one or more of the structuralunits (a), (b), (c), and (d); and (iv) at least one copolymer comprisingtwo or more of the structural units (a), (b), (c), and (d). Thesereaction mixtures may be induced to react to form novel, uncrosslinkedhybrid polymer or ceramer compositions which incorporate the at leastone organic electrophile comprising at least one organic monomer,oligomer, or polymer into the structure of the one or moremetal-containing polymers and which, in a subsequent step, may becrosslinked. In a preferred embodiment, the reaction product of the atleast one organic electrophile comprising at least one organic monomer,oligomer or polymer and the one or more metal-containing polymers may bea liquid which may be cured to a rigid solid by crosslinking afterprocessing the liquid into a desired shape. The cure may be effected byproviding crosslinking using an energy input using at least oneactivation means comprising, for example, thermal activation orradiation-induced activation to effect crosslinking through an ionic orradical-based crosslinking mechanism.

In a further preferred embodiment, the reaction product comprises sitesof organounsaturation such as alkenyl or alkynyl groups. Thus, whenR=alkenyl or alkynyl, these compositions may be crosslinked by supplyingan energy input in the form of, for example, thermal energy orradiation, such as ultraviolet radiation, microwave radiation orelectron beam radiation, to crosslink, to a desirable extent, the hybridpolymer or ceramer compositions. In this case, crosslinking occurs byactivating alkenyl-based or alkynyl-based polymerization of the alkenylor alkynyl groups within these compositions. When the reaction productcomprises a liquid, such crosslinking provides a mechanism for curing toa rigid solid, if desired, after processing the liquid into a desiredshape.

In another preferred embodiment of the present invention, thecompositions comprise reaction mixtures comprising (1) at least oneorganic electrophile comprising at least one organic monomer, oligomeror polymer comprising a plurality of organic, electrophilicsubstituents, and (2) at least one metal-containing polymer comprisingat least one of: (i) at least one metal-nitrogen polymer selected fromthe group consisting of silicon-nitrogen polymers, aluminum-nitrogenpolymers, and boron-nitrogen polymers comprising a multiplicity ofsequentially bonded repeat units of the form (a), (b), (c), and (d),recited below: ##STR7## respectively, where R, R', R", and R'"=hydrogen,alkyl, alkenyl, alkynyl or aryl and A=O or S; (ii) at least one mixtureof two or more metal-nitrogen polymers comprising two or more of thestructural units (a), (b), (c), and (d); (iii) at least onemetal-crosslinked metal-nitrogen polymer comprising one or more of thestructural units (a), (b), (c), and (d); and (iv) at least onemetal-nitrogen copolymer comprising two or more of the structural units(a), (b), (c), and (d), which, subsequent to reaction to form novelhybrid polymer or ceramer compositions, may be crosslinked to obtainhigh performance materials. In a preferred embodiment of the presentinvention, mixtures comprise either liquid metal-containing polymer,liquid organic electrophiles, or both liquid metal-containing polymersand liquid organic electrophiles. In a further preferred embodiment ofthe present invention, mixtures further comprise compositions whereinR=alkenyl or alkynyl, more preferably wherein the at least onemetal-containing polymer (e.g., the at least one metal-nitrogen polymer,the at least one metal-crosslinked metal-nitrogen polymer, the at leastone metal-nitrogen copolymer, etc.) may be present, for example, atgreater than about 10 wt % of the combined weight of the at least onemetal-containing polymer and the at least one organic electrophile andcomprises the repeat units (a), wherein R=vinyl, and even morepreferably wherein the at least one metal-containing polymer (e.g., theat least one metal-nitrogen polymer, at least one metal-crosslinkedmetal-nitrogen polymer, or at least one metal-nitrogen copolymer, etc.)comprises the repeat units (a), wherein R=vinyl, and R'=hydrogen.

In another preferred embodiment of the present invention, compositionsmay further comprise crosslinkable compositions comprising theuncrosslinked reaction products of a reaction mixture comprising (1) atleast one organic electrophile comprising at least one organic monomer,oligomer or polymer comprising a plurality of organic, electrophilicsubstituents, and (2) at least one metal-containing polymer comprisingat least one of: (i) at least one metal-nitrogen polymer selected fromthe group consisting of silicon-nitrogen polymers, aluminum-nitrogenpolymers, and boron-nitrogen polymers comprising a plurality ofsequentially bonded repeat units selected, for example, from the form(a), (b), (c), and (d), recited below: ##STR8## respectively, where R,R', R", and R'"=hydrogen, alkyl, alkenyl, alkynyl or aryl and A=O or S;(ii) at least one mixture of two or more metal-nitrogen polymerscomprising two or more of the structural units (a), (b), (c), and (d);(iii) at least one metal-crosslinked metal-nitrogen polymer comprisingone or more of the structural units (a), (b), (c), and (d); and (iv) atleast one metal-nitrogen copolymer comprising two or more of thestructural units (a), (b), (c), and (d), which may be crosslinked to ahigh performance material in a subsequent processing step. In apreferred embodiment, reacted compositions comprise compositions whichcomprise liquids. In a preferred embodiment of the present invention,compositions further comprise sites of organounsaturation such asalkenyl or alkynyl groups. In a preferred embodiment of the presentinvention, compositions further comprise a reaction product whereinR=alkenyl, more preferably wherein the at least one metal-containingpolymer (e.g., the at least one metal-nitrogen polymer, the at least onemetal-crosslinked metal-nitrogen polymer, the at least onemetal-nitrogen copolymer, etc.) is present at greater than about 10 wt %of the combined weight of metal-nitrogen polymer and the at least oneorganic electrophile and comprises the repeat units (a), whereinR=vinyl, and even more preferably wherein the at least onemetal-containing polymer (e.g., the at least one metal-nitrogen polymer,the at least one metal-crosslinked metal-nitrogen polymer, the at leastone metal-nitrogen copolymer, etc.) comprises the repeat units (a)wherein R=vinyl, and R'=hydrogen.

In another preferred embodiment of the present invention, compositionsmay further comprise the crosslinked product of an uncrosslinkedreaction product of a reaction mixture comprising (1) at least oneorganic electrophile comprising at least one organic monomer, oligomer,or polymer comprising a plurality of organic, electrophilicsubstituents, and (2) at least one metal-containing polymer comprisingat least one of: (i) at least one metal-nitrogen polymer selected fromthe group consisting of silicon-nitrogen polymers, aluminum-nitrogenpolymers, and boron-nitrogen polymers comprising a plurality ofsequentially bonded repeat units of the form (a), (b), (c), and (d),recited below: ##STR9## respectively, where R, R', R" and R'"=hydrogen,alkyl, alkenyl, alkynyl or aryl and A=O or S; (ii) at least one mixtureof two or more polymers comprising two or more of the structural units(a), (b), (c), and (d); (iii) at least one metal-crosslinkedmetal-nitrogen polymer comprising one or more of the structural units(a), (b), (c), and (d); and (iv) at least one metal-nitrogen copolymercomprising two or more of the structural units (a), (b), (c), and (d).

In a preferred embodiment of the present invention when R or R'=alkenylor alkynyl, these compositions may be crosslinked by supplying an energyinput in the form of, for example, thermal energy or radiation, such asultraviolet radiation, microwave radiation or electron beam radiation.The energy input may crosslink the hybrid polymer or ceramercompositions by activating alkenyl-based or alkynyl-based polymerizationof the alkenyl or alkynyl groups within these compositions. Thiscrosslinking effect is believed to be most advantageous when thecrosslinkable reaction product comprises a liquid, and it is desired toshape-stabilize the composition by crosslinking the shaped liquid to arigid solid. In a preferred embodiment of the present invention,compositions thus may further comprise a reaction product whereinR=alkenyl, more preferably wherein the at least one metal-containingpolymer (e.g., the at least one metal-nitrogen polymer, the at least onemetal-crosslinked polymer, the at least one metal-nitrogen) copolymer,etc., is present at greater than about 10 weight percent of the combinedweight of metal-nitrogen polymer and organic electrophile and comprisesthe repeat units (a), wherein R=vinyl, and even more preferably whereinthe at least one metal-containing polymer (e.g., at least onemetal-nitrogen polymer, at least one metal-crosslinked metal-nitrogenpolymer, or at least one metal-nitrogen copolymer, etc.) comprises therepeat units (a), wherein R=vinyl, and R'=hydrogen. In a preferredembodiment, R or R' may also comprise a group such as an epoxy oracrylate-based group which may provide for ionic crosslinking of thereacted hybrid polymer or ceramer composition. When Si--H bonds andvinyl groups are present in the uncrosslinked reacted composition, ahydrosilylation mechanism, for example, may be used to crosslink thereacted composition. Alternatively, the thermal decompositioncharacteristics of the metal-containing polymer backbone may be used togenerate the crosslinked structure once the reaction product of themetal-containing polymer with the at least one organic electrophile isobtained. Such mechanisms may be used when these polymers are used aspreceramic polymers (e.g., without combining them with the at least oneorganic electrophiles) and conversion to ceramic materials may occur bythermolytic crosslinking.

Although not required, it is desirable for the at least onemetal-containing polymer to comprise an amount of at least about 10 wt %or more of the total composition based on the combined weight ofmetal-nitrogen polymer and organic electrophile. Preferably, the atleast one metal-containing polymer comprises between about 10 weightpercent and 90 weight percent, and more preferably, at between about 15weight percent and about 65 weight percent.

The at least one organic electrophile comprising the organic monomers,oligomers, or polymers comprising a plurality of electrophilicsubstituents suitable for the practice of this invention is defined asorganic monomers, oligomers or polymers which contain a plurality of oneor more reactive groups which may attack the electron density of ametal-nitrogen bond (e.g., Si--N, Al--N, B--N bonds, etc.) of ametal-containing polymer, resulting in the breaking of these bonds and,subsequently, the formation of new bonds. Alternatively, when R'=H, theat least one organic electrophile comprising organic monomers,oligomers, or polymers may preferentially react at N--H bonds of the atleast one metal-containing polymer. Either mechanism provides for theincorporation of the at least one organic electrophile comprising atleast one organic monomer, oligomer, or polymer into the structure ofthe at least one metal-containing polymer. In a preferred embodiment,the at least one organic electrophile comprises a liquid thus increasingthe probability for reaction of the at least one organic electrophilecomprising at least one organic monomer, oligomer or polymer with the atleast one metal-containing polymer comprising one or more metal-nitrogenpolymers.

Typical examples of electrophilic groups which are suitableelectrophilic substituents for the multifunctional organic electrophileinclude groups containing, for example, the following bonding schemes:##STR10## and the like.

Typical organic monomers, oligomers, or polymers suitable for thepractice of this invention include, for example, multifunctional organicisocyanates, multifunctional compounds comprising amide linkages such aspolyamides, multifunctional compounds comprising imide linkages such aspolyimides multifunctional epoxides, multifunctional compoundscomprising ester linkages, such as polyacrylates, polycarbonates,polyvinylacetates, or polyesters, multifunctional esters such asdimethyl adipate, diallyl phthalate, and diethylene glycol bisallylcarbonate, and multifunctional organic acids such as polyacrylic acid.

Since in a preferred embodiment of the invention compositions comprisemetal-containing polymers which contain Si--N bonds, it is informativeto describe the reactions of typical monomeric electrophiles with suchmetal-containing polymers.

Monofunctional isocyanates are known to react with silicon-nitrogenpolymers by inserting into the Si--N bond of the polymers as shown inEquation 1: ##STR11##

Such reactivity is disclosed in U.S. Pat. No. 4,929,704 entitled"Isocyanate- and Isothiocynate-Modified Polysilazane CeramicPrecursors", which issued in the name of Schwark, on May 29, 1990; U.S.Pat. No. 5,001,090 entitled "Silicon Nitride Ceramics from Isocyanate-and Isothiocyante-Modified Polysilazanes", which issued in the name ofSchwark, on Mar. 19, 1991; and U.S. Pat. No. 5,021,533 entitled"Crosslinkable Poly(thio)ureasilazane Composition Containing a FreeRadical Generator", which issued in the name of Schwark, on Jun. 4,1991. This mode of reactivity is distinctly different from that observedby Fink et al. in U.S. Pat. No. 3,239,489, for example, wherein apolysilazane containing, as an enabling feature, a N--H bond reacts withan isocyanate group exclusively at the N--H bond to give the followingbonding scheme: ##STR12##

In the present invention, polysilazanes comprising no N--H bonds aresuitable since reaction of the isocyanate occurs at the Si--N bond.Moreover, it has been discovered that reactivity at Si--N bonds in suchsystems can be promoted by choosing polysilazanes which comprisesterically undemanding substituents on the silicon atom; especiallypreferred are, therefore, polysilazanes comprising hydrogen substituentson the silicon atom. Polysilazanes comprising Si--H bonds are notemployed by Fink et al. Indeed, Fink et al. excludes all polysilazanescomprising mobile hydrogen atoms. Schwark, in U.S. Pat. No. 4,929,704,has disclosed that hydrogen atoms bonded to silicon in polysilazanes,when employed in such systems, are mobile hydrogen atoms.

Monofunctional amides, imides and esters (which comprise theelectrophilic C═O moiety) are also known to react with silicon-nitrogenpolymers. While not wishing to be bound by any particular theory orexplanation, it is believed that the reaction proceeds by insertion ofthe C═O bond of amide, imide or ester into the Si--N bond of the polymeras shown in Equation 2 for a monofunctional amide or ester: ##STR13##where R is an organic radical or hydrogen and where G=NR1R² or OR³, andR¹, R² and R³ are independently selected from at least one of organicradicals or hydrogen.

Such reactivity is disclosed in U.S. Pat. No. 5,032,649 entitled"Organic Amide-Modified Polysilazane Ceramic Precursors", which issuedin the name of Schwark, on Jul. 16, 1991; and U.S. Pat. No. 5,155,181entitled "(Thio)amide-Modified Silazane Polymer Composition Containing aFree Radical Generator", which issued in the name of Schwark, on Oct.13, 1992.

Thus, in the case of the reaction of a silicon-nitrogen polymer with anorganic isocyanate, a simple addition of the electrophilic N═C bondacross the Si--N bond is believed to occur. Similarly, when asilicon-nitrogen polymer reacts with an organic amide, imide or ester,reaction is believed to occur by insertion of the electrophile C═O bondacross the Si--N bond.

In both cases an Si--N bond is broken and in both cases newsilicon-heteroatom bonds form which comprise a silicon atom from thesilicon-nitrogen polymer and a nitrogen or oxygen atom originating inthe monofunctional, organic monomer containing the electrophilicsubstituent.

On the other hand, when silicon-nitrogen polymers comprisingnitrogen-hydrogen bonds react with monofunctional organic epoxidesreaction may occur at the N--H bond of the silicon polymer asillustrated by Equation 3: ##STR14## as well as at the Si--N bond of thesilicon nitrogen polymer as illustrated by Equation 4: ##STR15##

Again, the reaction with a monofunctional organic epoxide would appearto be a simple addition reaction wherein new bonds are formed whichincorporate the organic reactant into the silicon-nitrogen polymerstructure. The results of infrared studies of the reaction ofmultifunctional epoxides and polysilazanes over time have shown that thereaction mode depicted in Equation 4 may be predominant. Subsequentcrosslinking reactions within the co-reacted compositions shown inEquations 1 through 4 are believed to then occur.

Similar reactivity has been observed for boron-nitrogen polymers as, forexample, documented in the reaction of a borazine with monofunctionalisocyanates reported by, for example, Cragg, R. H., and M. F. Lappert,J. Chem. Soc. (London) 1964, 2108 or Beyer, H., J. W. Dawson, H. Jenneand K. Niedenzu, J. Chem. Soc. (London), 1964, 2115 and illustrated byEquation 5:

    [--BN(C.sub.2 H.sub.5).sub.2 --NH--].sub.3 +3RNCO→{--B[NR--CO--N(C.sub.2 H.sub.5).sub.2 ]--NH--}.sub.3,Equation 5

or the reaction of a dialkyl aluminum amine with monofunctionalisocyanates (reported by, for example, T. Hirabayashi, H. Imaeda, K.Itoh, S. Sakai and Y. Ishii, J. Organometal. Chem., 19 (1969) 299) andillustrated by Equation 6:

    (C.sub.2 H.sub.5).sub.2 AlN(CH.sub.3).sub.2 +RNCO→RN═C[N(CH.sub.3).sub.2 ]--OAl(C.sub.2 H.sub.5).sub.2.Equation 6

The organic, electrophilic compositions suitable for the practice of thepresent invention, however, are typically not monofunctional. Thesecompositions comprise at least one organic electrophile comprising atleast one organic monomer, oligomer, or polymer comprising a pluralityof electrophilic substituents For the purposes of this invention, theterm monomer is defined as a chemical compound which comprises only onerepeat unit, the term oligomer is defined as a chemical compound whichcomprises a few repeat units (generally from about 2 to about 10), andthe term polymer is defined as a compound which comprises a large numberof repeat units (generally greater than about 10). A multiplicity ofelectrophilic substituents is defined as at least two reactive groupswithin the same organic monomer, oligomer, or polymer which causemetal-nitrogen bond (e.g., the Si--N bond in a silicon-nitrogencoreactant polymer) or nitrogen-hydrogen bond (N--H bond) scissionwithin a metal-nitrogen coreactant polymer. While not essential for thepurposes of this invention, it may be desirable that the at least oneorganic electrophile comprising at least one organic monomer, oligomer,or polymer comprise about 10 wt % or more of the combined weight of theat least one organic electrophile and the at least one metal-containingpolymer (e.g., the metal-nitrogen polymer). Preferably, the at least oneorganic monomer, oligomer, or polymer comprises about 30 wt % or more,even more preferably between about 35 weight percent and about 85 weightpercent, and even more preferably, between about 40 weight percent andabout 70 weight percent.

Suitable monomeric, oligomeric, or polymeric organic isocyanates whichmay be used according to this invention include, but are not limited to,aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclicpolyisocyanates and mixtures thereof. Suitable polyisocyanates which maybe used in the process of this invention include, but are not limitedto, for example, p,p'-diphenylmethane diisocyanate, phenylenediisocyanate, chlorophenylene diisocyanate, tolylene diisocyanate,m-xylylene diisocyanate, benzidine diisocyanate, naphthylenediisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate,hexamethylene diisocyanate, decamethylene diisocyanate, and thiodipropyldiisocyanate. Other polyisocyanates, polyisothiocyanates and theirderivatives may be equally employed. Fatty diisocyanates may be equallyemployed. Another group of suitable polyisocyanates are so-calledmodified polyisocyanates, i.e., polyisocyanates containing carbodiimidegroups, allophanate groups, isocyanurate groups, urea groups, amidegroups, imide groups, or biuret groups. Polyisocyanates suitable formodification in this way include, for example, aliphatic,cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates.It is generally preferred to use commercially readily availablepolyisocyanates, e.g. tolylene-2,4- and -2,6-diisocyanate and anymixtures of these isomers, polyphenyl- polymethylene-isocyanatesobtained by aniline-formaldehyde condensation, followed by phosgenation,and polyisocyanates which contain carbodiimide groups, urethane groups,allophanate groups, isocyanurate groups, urea groups, imide groups orbiuret groups.

The reaction of a metal-nitrogen polymer with the above-mentionedmultifunctional isocyanate monomers, oligomers, or polymers may proceedwith or without a catalyst. Preferred catalysts comprise, for example,organic tin compounds. The organic tin compounds preferably comprise tinsalts of carboxylic acids such as tin acetate, tin octoate, tin ethylhexoate and tin laurate and the dialkyl tin salts of carboxylic acidsuch as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tinmaleate or dioctyl tin diacetate.

Bases which contain nitrogen such as tetraalkyl ammonium hydroxides,alkali metal hydroxides such as sodium hydroxide, alkali metalphenolates such as sodium phenolate or alkali metal alcoholates such assodium methylate may also be used as a catalyst. Hexahydrotriazines arealso suitable catalysts.

Silaamines with carbon-silicon bonds may also be used as catalysts, suchas those silaamines described in German Patent No. 1,229,290, forexample, 2,2,4-trimethyl-2-silamorpholine or1,3-diethylaminomethyl-tetramethyldisiloxane. The disclosure of GermanPatent No. 1,220,290 is incorporated herein by reference.

Other catalysts may include tertiary amines such as triethylamine,tributylamine, triethylenediamine, N-methyl-morpholine,N-ethyl-morpholine, N-cocomorpholine,N,N,N',N'-tetramethylethylenediamine, 1,4-diaza-bicyclo-(2,2,2)-octane,N-methyl-N'-dimethylaminoethyl piperazine, N,N-benzylamine,bis-(N,N-diethylaminoethyl)-adipate, N,N-diethyl benzylamine,pentamethyl diethylenetriamine, N,N-dimethyl cyclohexylamine,N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-beta-phenylethylamine, 1,2-dimethyl imidazole, 2-methyl imidazole,hexahydrotriazine derivatives, triethanolamine, triisopropanolamine,N-methyldiethanolamine, N-ethyl-diethanolamine,N,N-dimethyl-ethanolamine, and tertiary amine reaction products withalkylene oxides such as propylene oxide and/or ethylene oxide.

Other examples of catalysts which may be used according to the inventionand details of the catalysts may be found in Kunststoff-Handbuch, VolumeVII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966,e.g., on pages 96 to 102.

The catalyst may generally be used in a quantity of between about 0.001%and about 10% by weight, based on the quantity of isocyanate, and may beadded simultaneously with the other components.

Suitable monomeric, oligomeric, and polymeric esters which may be usedaccording to this invention include, but are not limited to, forexample, difunctional esters such as dimethyl adipate, diethylsuccinate, and dimethyl glutarate as well as the polyesters of aromaticdibasic acids and alkylene glycols. The polyesters also may be derivedfrom, for example, a mixture of aromatic dicarboxylic acids, and one ormore diols. Examples of symmetrical aromatic dicarboxylic acids includeterephthalic acid, dibenzoic acid, ethylene bis-p-oxybenzoic acid,tetramethylene bis-p-oxybenzoic acid, and 2,6-naphthalic acid. Otheraromatic dicarboxylic acids which can be used in conjunction with thesymmetrical dicarboxylic acid include, for example, o-phthalic acid,isophthalic acid, etc.

Representative glycols which may be reacted with the dibasic acids toform the desired polyesters include, for example, ethylene glycol, 1,2-and 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol,polyethylene glycol, etc.

Also useful in the present invention are polyesters prepared from, forexample, acyclic dicarboxylic acids and glycols such as those describedabove. Specific examples of the acyclic dicarboxylic acids suitable toprepare the polyesters useful in the practice of this invention includeadipic acid, pimelic acid, suberic acid, azelaic acid, oxy-dibutyricacid, sebacic acid, 5-oxa-1,10-decanedioic acid, 4-n-propyl subericacid, dodecane dioic acid, tridecane dioic acid, etc.

Particularly useful combinations of aromatic and aliphatic dicarboxylicacids used in the preparation of copolyesters useful in the presentinvention include: terephthalic acid, azelaic acid andpentamethyleneglycol; terephthalic acid, isophthalic acid and adipicacid; terephthalic acid, isophthalic acid, adipic acid and sebacic acid;terephthalic acid, isophthalic acid, adipic acid and ethylene glycol;etc. Copolyesters of such mixtures may be prepared directly from theabove-identified dicarboxylic acids, or the copolyesters may be preparedfrom the lower alkyl esters of said dicarboxylic acids such as dimethylterephthalate, dimethyl isophthalate, dimethyl sebacate, dimethyladipate, etc. Procedures for preparing copolyesters useful incombination with the metal-containing polymers in this invention aredescribed in, for example, U.S. Pat. No. 2,623,033 entitled "ElasticCopolyesters and Process", which issued in the name of Snyder, on Dec.30, 1952, and U.S. Pat. No. 2,892,747 entitled "New Linear Copolyesters,Products Containing Same and Process Therefor", which issued in the nameof Dye, on Jun. 30, 1959. The entire disclosures of both of thesepatents are specifically incorporated herein by reference, includingtheir disclosure of linear copolyesters derived at least in part fromsymmetrical aromatic dicarboxylic acids.

Suitable polyester amides and polyamides include, but are not limitedto, for example, predominantly linear condensates obtained from, forexample, polyvalent saturated and unsaturated carboxy acids or theiranhydrides and polyvalent saturated and unsaturated amino alcohols,diamine, polyamines and mixtures thereof.

Suitable polyimides include, but are not limited to, for example,predominantly linear condensates obtained from the reaction of, forexample, a multifunctional acid and/or acid anhydride and a difunctionalaromatic amine. The multifunctional acid and/or acid anhydride mayfeature the characteristic groups comprising, for example, trimelliticacid/anhydride (TMA), pyromellitic dianhydride (PMA), benzophenonetetracarboxylic anhydride (BPA), maleic anhydride (MA), etc. Thedifunctional aromatic amine may feature the characteristic groupscomprising, for example, 4,4' diamino diphenyl methane (MDA), 4,4'diamino diphenyl ether (PEA), m-phenylene diamine (MPA), benzidine orp-phenylene diamine (PPA), and, sometimes, aromatic diisocyanates, forexample, 4,4' diisocyanato diphenyl methane (MDI). Some examples ofsuitable polyimides include, for example, low molecular weightbismalemides, bisnadimides, etc.

The monomeric, oligomeric, or polymeric carboxylic acid may bealiphatic, cycloaliphatic, aromatic and/or heterocyclic and may besubstituted, for example, with halogen atoms and may be unsaturated;examples include compounds made from derivatives of: succinic acid,adipic acid, sebacic acid, azelaic acid, phthalic acid, phthalic acidanhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, endomethylene tetrahydrophthalic acid anhydride,glutaric acid anhydride, fumaric acid, maleic acid, maleic acidanhydride, dimeric and trimeric fatty acids such as oleic acid,optionally mixed with monomeric fatty acids, and dimethylterephthalate.

Suitable monomeric, oligomeric, or polymeric organic epoxides which maybe used according to the present invention may be of the ether or estertypes, although the ether type epoxy resins are preferred. Examples ofester-type epoxy resins include polyglycidyl esters obtainable byreaction of a compound containing two or more carboxylic acid groups permolecule with epichlorohydrin or glycerol dichlorohydrin in the presenceof an alkali. Such polyglycidyl esters may be derived from aliphaticpolycarboxylic acids, e.g. succinic acid, glutaric acid, adipic acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, or dimerized ortrimerized linoleic acid; from cycloaliphatic polycarboxylic acids suchas tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid,hexahydrophthalic acid, and 4-methylhexahydrophthalic acid; and fromaromatic polycarboxylic acids such as phthalic acid, isophthalic acid,and terephthalic acid.

Ether-type epoxy resins may be obtained by reaction of a compoundcontaining at least two free alcoholic hydroxyl and/or phenolic hydroxylgroups per molecule with an epihalohydrin under alkaline conditions, orin the alternative, in the presence of an acidic catalyst withsubsequent treatment with an alkali. The products of such reactionsinstead of being single simple compounds are generally complex mixturesof glycidyl polyethers. These ethers may be made from acyclic alcoholssuch as ethylene glycol, diethylene glycol, and higherpoly(oxyethylene)glycols, propane-1,2-diol andpoly(oxypropylene)glycols, propane-1,3-diol,poly(oxytetramethylene)glycols, pentane-1,5-diol, hexane-2,4,6-triol,glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, andpolyepichlorohydrins; from cycloaliphatic alcohols such as resorcinol,quinitol, bis(4-hydroxycyclohexyl)methane, and2,2-bis(4-hydroxycyclohexyl)propane, and from alcohols having aromaticnuclei, such as N,N-bis(2-hydroxyethyl)aniline andp,p'-bis(2-hydroxyethylamino)diphenylmethane. Alternatively, they may bemade from mononuclear phenols, such as resorcinol and hydroquinone, andfrom polynuclear phenols, such as bis(4-hydroxyphenyl)methane (otherwiseknown as Bisphenol "F"), 4,4'-dihydroxydiphenyl,bis(4-hydroxyphenyl)sulphone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane, (otherwise known as Bisphenol "A"),2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, and novolacs formed fromaldehydes such as formaldehyde, acetaldehyde, chloral, andfurfuraldehyde, with phenol itself, and phenol substituted in the ringby chlorine atoms or by alkyl groups such as 4-chlorophenol,2-methylphenol, and 4-tert-butylphenol.

The epoxy resins may have either a mixed aliphatic-aromatic or anexclusively non-benzenoid (i.e., aliphatic or cycloaliphatic) molecularstructure. The mixed aliphatic-aromatic epoxy resins generally may beprepared by the well-known reaction of a bis-(hydroxy-aromatic)alkane ora tetrakis-(hydroxy-aromatic)alkane with a halogen-substituted aliphaticepoxide in the presence of a base such as, for example, sodium hydroxideor potassium hydroxide.

In one preferred embodiment, the epoxy resins comprise diglycidyl ethersof bisphenols, especially Bisphenol "A". These diglycidyl ethers may bemade by reacting epichlorohydrin with Bisphenol "A" in the presence ofan alkaline catalyst. By controlling the operating conditions andvarying the ratio of epichlorohydrin to Bisphenol "A", products ofdifferent molecular weight can be made.

Other usable epoxy resins include the diglycidyl ethers of otherbisphenol compounds such as bisphenol B, F, G, and H.

Another class of epoxy resins useful in the present invention comprisethe epoxidized novolacs, particularly the epoxy cresol and epoxy phenolnovolacs. These may be produced by reacting a novolac resin, usuallyformed by the reaction of orthocresol or phenol and formaldehyde withepichlorohydrin.

Epoxy resins derived from non-benzenoid materials such as aliphatic orcycloaliphatic hydroxy-containing compounds also may be utilized in thepresent invention. Epoxy resins having non-benzenoid molecularstructures generally are referred to in the art as being aliphatic epoxyresins or cycloaliphatic epoxy resins. Cycloaliphatics may be producedby the peracetic epoxidation of cyclic olefins and by the condensationof an acid such as tetrahydrophthalic with epichlorohydrin, followed bydehydrohalogenation. The aliphatic epoxy resins may be prepared byreacting hydroxy-containing aliphatic and cycloaliphatic compounds suchas aliphatic diols and triols. For example, ethylene glycol or glycerolmay be reacted with a halogen-substituted aliphatic epoxide such asepichlorohydrin to form liquid epoxy resins characterized by viscositieswhich are lower than epoxy resins derived from aromatic hydroxycompounds. When cured, such aliphatic epoxy resins may not be as brittleas the aromatic epoxy resins, and in many instances, exhibit elastomericproperties.

The reaction of a metal-containing polymer comprising a metal-nitrogenpolymer with the above-mentioned epoxide-substituted monomers,oligomers, or polymers may proceed with or without a catalyst.Representative examples of such catalysts include, for example, LewisAcids such as BF₃ and its complexes; alcohols, such as methanol,ethylene glycol, glycerol, and thiethanolamine; phenols, such as phenol,Bisphenol "A", resorcinol, m-nitrophenol, 2,4-dinitrophenol,2-chlorophenol, 2,4,5,-hydroxyphenyl)propane, 2,4,5,6-tetrachlorophenol,pentachlorophenol, p-chlororesorcinol, p-chlorophenol, andp-bromophenol; carboxylic acids, such as benzoic acid, salicylic acid,and lactic acid; and tertiary amines.

When such multifunctional organic monomers, oligomers, or polymers arereacted with metal-containing polymers of the type described above,compositions containing organic segments are believed to occur. When thetotal fraction of the at least one organic electrophile comprising theat least one multifunctional organic monomer, oligomer, or polymer usedin the reaction mixture is high, reaction products exhibiting acombination of the desirable properties characteristic of typicalorganic polymers as well as the desirable properties characteristic ofthe at least one metal-chlororesorcinol, polymer are obtained. Forexample, while polysilazanes have favorable thermal stability, they areoften not very strong materials. By co-reacting, for example, apolysilazane and an organic diepoxide, however, a composition having,for example, good strength as well as good thermal stability may beobtained. Inorganic fillers which are not very compatible with typicalorganic polymer resins, surprisingly, have also been found to becompatible with the newly discovered hybrid polymer or ceramercompositions.

The reaction to form the hybrid polymers or ceramers may be accomplishedwith or without solvent, as a suspension or as an emulsion. Typically,and in a preferred embodiment of this invention, the reaction may beperformed using liquid components and without any solvent. When asolvent is used, the solvent is typically non-reactive to the componentsbeing reacted. Typical solvents suitable for the practice of thisinvention include non-protic, organic solvents such as hydrocarbon andether solvents. Representative of such solvents are toluene, xylene,benzene, hexane, heptane, tetrahydrofuran, and diethyl ether, althoughthis list is meant to be representative and not limiting.

While many metal-containing polymers may be suitable for suchmodification, a particularly preferred embodiment of the presentinvention rests on the surprising behavior and properties obtained byreacting alkenyl-substituted silicon-nitrogen polymers with a largefraction of an at least one organic electrophile comprising at least oneorganic monomer, oligomer, or polymer comprising a plurality ofelectrophilic substituents, and then introducing further crosslinkinginto the reaction product so obtained by inducing alkenyl crosslinkingby supplying an energy input, or by hydrosilylation. Preferredsilicon-nitrogen polymers suitable for the practice of this inventionthus comprise liquid metal-nitrogen polymers having the repeat units:##STR16## In each of (a) and (d) above, R=alkenyl and R'=H (as shown)and R", R'" and A are defined as above.

Such silicon-nitrogen polymers may be, for example, a polysilazane,polyureasilazane, or poly(thio)ureasilazane, although polysilazanes andpolyureasilazanes are preferred. While this list is representative ofthe types of silicon-nitrogen polymers which may be used in the practiceof this invention, however, the list is not meant to be exhaustive. Thesilicon-nitrogen polymers suitable for the practice of this inventionmay include cyclic oligomers and ring-based and linear polymers. Lowmolecular weight, liquid silicon-nitrogen polymers are preferred, sincethe co-reactant organic monomers, oligomers, or polymers used in thepresent invention may often be miscible with, or soluble in liquidsilicon-nitrogen polymers and the resulting mixture may be processedwithout the use of a solvent vehicle. Preferably, the silicon-nitrogenpolymers used have a number average molecular weight (M_(n)) of lessthan about 5,000 and, more preferably, less than 2,000. Narrow molecularweight distributions (M_(w) /M_(n) <about 3.0) are preferred. Typically,it is preferable to include such polymers at greater than about 10 wt %of the combined weight of the composition comprising the at least onemetal-containing polymer and the at least one organic electrophile.

Representative, low molecular weight, liquid silicon-nitrogen polymerscomprising silyl vinyl groups have been shown in the past to convertrapidly to rigid, solid materials through vinyl crosslinking reactions.Such crosslinking may occur rapidly (e.g., <1 minute) at modesttemperature (e.g., <150° C.) using free radical generator additives.Such crosslinking is taught in, for example, U.S. Pat. No. 4,929,704entitled "Isocyanate- and Isothiocyante-Modified Polysilazane CeramicPrecursors", which issued in the name of Schwark, on May 29, 1990; U.S.Pat. No. 5,001,090 entitled "Silicon Nitride Ceramics from Isocyanate-and Isothiocyante-Modified Polysilazanes", which issued in the name ofSchwark, on Mar. 19, 1991; U.S. Pat. No. 5,021,533 entitled"Crosslinkable Poly(thio)ureasilazane Composition Containing a FreeRadical Generator", which issued in the name of Schwark, on Jun. 4,1991; U.S. Pat. No. 5,032,649 entitled "Organic Amide-ModifiedPolysilazane Ceramic Precursors", which issued in the name of Schwark,on Jul. 16, 1991; and U.S. Pat. No. 5,155,181 entitled"(Thio)amide-Modified Silazane Polymer Composition Containing a FreeRadical Generator", which issued in the name of Schwark, on Oct. 13,1992; U.S. Pat. No. 5,155,181 entitled "(Thio)amide-Modified SilazanePolymer Composition Containing a Free Radical Generator", which issuedin the name of Schwark, on Oct. 13, 1992; and U.S. Pat. No. 4,722,988entitled "Organopolysilazane Composition Containing Free RadicalGenerators and Capable of Being Crosslinked by an Energy Input", whichissued in the names of Porte et al., on Feb. 2, 1988. Hydrosilylationcrosslinking mechanisms have also been demonstrated using added metalcatalysts such as chloroplatinic acid. Such crosslinking is taught in,for example, U.S. Pat. No. 4,689,252 entitled "Polysilazane Compositionwhich can Crosslink in the Presence of a Metal Compound Catalyzing aHydrosilylation Reaction", which issued in the names of Lebrun et al.,on Aug. 25, 1987.

Suitable free radical generators may include, but are not limited to,organic and inorganic peroxides, alkali metal persulfates, ammoniumpersulfate, redox systems, aliphatic azo compounds, organic andinorganic peroxides with organic and inorganic metal compounds. Suitableperoxide initiators include, but are not limited to, hydrogen peroxideand acyl or aryl peroxides such as p-menthane hydroperoxide, ethylketone peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, acetylbenzyl peroxide, p-chlorobenzoyl peroxide, alkoxy benzoyl peroxide,lauroyl peroxide, dicaproyl peroxide, crotonyl peroxide, di-tert-alkylperoxide, di-tert-butyl diphosphate peroxide, peracetic acid, cyclohexylhydroperoxide, and dicumyl peroxide. Suitable persulfates includeammonium persulfate, potassium persulfate and sodium persulfate. Anysuitable commonly known redox systems known to those who are skilled inthe art may be used. Other initiator systems may be used such asperoxides with metal compounds as activators such as ethyl ketoneperoxide with cobalt naphthenate, potassium persulfate with ferricsulfate or cupric sulfate and benzoyl peroxide with a tertiary amineactivator such as N,N-dimethyl aniline.

The specific alkenyl-substituted compositions, which are a particularlypreferred embodiment of the present invention, generally comprise thereaction product of an at least one organic electrophile comprising atleast one organic monomer, oligomer, or polymer comprising a pluralityof electrophilic substituents and a silicon-nitrogen polymer comprisingthe repeat units recited below: ##STR17## In each of (a) and (d) above,R=alkenyl, R'=H (as shown), and R", R'", and A are defined as above, arethus characterized in their ability to crosslink further through thesilyl alkenyl groups, for example, by an energy input, or free radicalmechanisms, or by a hydrosilylation mechanism. More preferred arereaction products which convert from a liquid to a rubbery or rigidsolid upon vinyl crosslinking. Even more preferred are compositionswhich convert from a low viscosity liquid (e.g., <5,000 cp) to a rubberyor rigid solid upon vinyl crosslinking. The energy input may be providedby supplying radiation, for example, in the form of ultraviolet (UV)radiation, electron beam radiation, laser or gamma radiation, or thermalenergy to the composition. In a preferred embodiment of the presentinvention, such polymers comprise at least about 10 weight percent ofthe combined weight of at least one the metal-containing polymer and theat least one organic electrophile.

It has also been unexpectedly discovered that by selecting amultifunctional organic electrophile of the appropriate activity, theheat generated from the reaction of the at least one organicelectrophile with a silicon-nitrogen polymer comprising R=vinyl to forman uncrosslinked hybrid polymer or ceramer may cause spontaneouscrosslinking of the vinyl groups within the co-reacted composition. Avery hard, rigid object may thus be obtained in a matter of severalminutes merely by admixing, for example, a liquid diisocyanate and a lowmolecular weight, liquid, vinyl-substituted polysilazane orpolyureasilazane at about room temperature. Self-initiated crosslinkingmay be especially effective when a free radical generator, such as, forexample, a peroxide or an azo compound is added to the reaction mixture,so that the heat generated in the reaction of the organic electrophilewith the silicon-nitrogen polymer initiates decomposition of the freeradical generator to provide a high concentration of free radicals. Freeradical addition may promote rapid vinyl crosslinking at relatively lowtemperatures in a very short period of time (e.g., <5 minutes). In theabsence of a large heat of reaction, radiation or thermal energy from anexternal source may be provided. Such thermal energy may be provided by,for example, simple convective heating or by induction, or byirradiation using a radiation source such as an electron beam or amicrowave.

The uncrosslinked compositions of the present invention may be useful ascurable coatings, infiltrants for porous bodies, or as low viscositymolding compositions suitable for injection molding, reaction injectionmolding (RIM), or pour molding of three dimensional objects, or for usein a variety of alternative forming techniques such as pulltrusion,extrusion, blow-molding, resin transfer molding, prepreging, casting,compression molding, etc.

One particularly useful molding technique discussed above comprisesreaction injection molding, commonly called "RIM". Reaction injectionmolding comprises a method for rapid production of complex plastic partsdirectly from relatively low viscosity monomers or oligomers. Theseliquids are combined by impingement mixing just as they enter a mold fordefining at least a portion of the complex plastic parts. Mold pressuresare typically very low. Solid polymer forms by crosslinking as a resultof impingement mixing and complex parts may often be demolded in lessthan about one minute. In the present invention, RIM may be accomplishedusing an at least two stream process in which at least one streamcontains at least one organic electrophile, for example, an isocyanate,and at least a second stream contains at least one metal-containingpolymer, such as, for example, a polyureasilazane.

Another useful molding technique comprises extrusion. Extrusioncomprises a process for continuously shaping a fluid polymer through atleast one orifice of an extrusion die and subsequently solidifying thepolymer into a product extrudate of substantially constant crosssection. Extrusion products include, for example, filaments of circularcross-section, profiles of irregular cross section, axisymmetric tubesand pipes, flat products such as films or sheets, etc. Mixtures ofhybrid polymers or ceramers, fillers, additives, etc. may be prepared byextrusion according to the methods of the present invention.

An additional useful molding technique comprises casting. Castingincludes any of a number of related processing methods, generallyinvolving the polymerization of a liquid resin such that at least onesurface of the resin is shaped to correspond to the shape of at leastone surface of a product and the resin and product are subjected,typically, to minimal stresses (e.g., atmospheric pressure, gravityflow, slow chemical reaction, moderate temperature, etc.) duringprocessing. Casting includes cases where inserts (inclusions) and/orfillers or reinforcements are at least partially and/or substantiallycompletely surrounded by a polymeric matrix (for example, encapsulation,embedment, potting, etc.), to assure positioning, thermal or electricalinsulation, environmental protection, and the like. In the presentinvention at least one organic electrophile such as, for example, anepoxy may be mixed in a vessel with at least one metal-containingpolymer and cast by pouring into, for example, an open mold.

Another useful molding technique comprises compression molding.Compression molding includes pressing or squeezing at least onedeformable material between at least two pieces of a heated mold,thereby transforming the material into at least one solid product underthe effect of the elevated mold temperature. Compression moldingtemperatures may range from about 140° C. to about 220° C.; moldpressures may vary from about 500 pounds per square (psi) to about10,000 psi; curing times may vary from minutes to hours. Transfermolding is related to compression molding in that a softenedtemperature-activated thermosetting polymer may be transferred throughat least one narrow gate into at least one closed cavity of a heatedmold and then cured to a solid state.

Another molding technique comprises injection molding. Injection moldingrelates to a process which involves the rapid pressure filling of atleast one mold cavity with a fluid material, followed by thesolidification of the fluid material into a product. In the presentinvention, for example, at least one mixture of at least one liquidmetal-containing polymer such as, for example, a polyureasilazane and atleast one organic monomer, oligomer or polymer comprising a plurality oforganic, electrophilic constituents, for example, an isocyanate, may beinjected under pressure into at least one cavity of a closed mold. Thepolymer cures to a rigid solid in the at least one cavity of the closedmold.

The compositions, for example, molded articles and coatings, of thepresent invention may be unfilled or filled with at least one filler orreinforcement. The at least one filler comprises either isotropic oranisotropic materials. Average particle diameters of filler orreinforcements used in the formation of compositions of the presentinvention can be as small as about 0.03 micron or less to about 1500microns or more. The specific size or size distribution used is afunction of the purpose of the filler or reinforcement. For example,when the filler or reinforcement is used to pigment the composition,submicron filler may be appropriate; however, when the filler orreinforcement is used to enhance the strength of the composition,fillers having average particle diameters of about one micron or less toabout 500 microns or more may be appropriate. The amount of filler orreinforcement used to form the compositions may be any that may berequired to achieve the properties desired in the compositions. Theseamounts may be as little as about 0.5 weight percent or less to about99.5 weight percent or more. Preferred amounts may range from about 10weight percent to about 90 weight percent. More preferred amounts mayrange from about 20 weight percent to about 85 weight percent. Even morepreferred amounts may range from about 25 weight percent to about 75weight percent. Thus, fillers includes either single constituents ormixtures of constituents which are either chemically reactive or whichare substantially non-reactive with and/or of limited solubility in thehybrid polymers or ceramer matrix materials such as, for example,particulate, whiskers, platelets, or even continuous fiber, etc.Continuous fiber fillers may be incorporated as uniaxial arrays,non-woven form, or woven form, although any means or geometry of fiberincorporation applies. For instance, stacked, woven fiber laminates maybe formed by impregnating woven fiber mat with at least one compositionof the present invention, stacking, and subsequently curing.Infiltration of liquid compositions of the present invention intothree-dimensional woven preforms may also possible. Fibrous fillersinclude chopped and/or continuous metals, glass, carbon or graphite,polymer (e.g., aramid) and ceramic fibers (although this list is meantto be non-limiting). The fiber reinforcements may be in the form ofyarn, woven yarn, fabric, roving, woven roving, continuous strand mat,chopped strand mat, woven roving/chopped strand mat combination and thelike. The at least one fiber or reinforcement may be introduced in themanner of bier preforms, fiber prepregs, bulk molding or sheet moldingcompounds which result from the mixing of chopped fibers with the resinsystem, hand lay-up, spray-up, filament winding which involves themechanical wrapping of resin-impregnated continuous filaments over amandrel, pulltrusion, mechanical and manual fiber placement, and resintransfer molding (also called resin injection molding) which involvesthe placement of a well-bound fiber mat into a cavity of a mold followedby introduction of a low-viscosity thermosetting resin into the cavityunder moderate pressure. For example, an embodiment of the presentinvention involves the hand lay-up of several plies of woven glass matin a mold cavity followed by the casting of a liquid organicelectrophile/metal-containing polymer reaction mixture onto the fibermats so that the liquid mixture permeates the pores in the fiber mat.The liquid polymer cures to a solid in the mold resulting in a strong,rigid fiber-reinforced polymer matrix.

These various molding processes may be modified within certain processlimitations depending upon the physical state, solid, or liquid, of themonomer, oligomer, or polymer molding reagents and the above examplesare intended only as illustrations and not as limiting conditions.

Molded objects prepared by the present invention are useful in sportinggoods applications such as golf clubs, tennis racquets, skate wheels,watercraft bodies, housing, and propellers, snowmobile bodies, sailboards and the like; automotive applications such as fenders, hoods, andbody panels; aerospace applications such as radomes, structuralcomposites; industrial uses such as wear parts in mining, coal, or orehandling such as pump and chute liners.

The compositions of the present invention may also be used as surfacemodifiers for compatibilizing inorganic/organic interfaces in compositematerials, or as binders for polymer, mineral, ceramic or metal fillerfor fabricating either monoliths or composite materials. Theuncrosslinked compositions may be either unfilled or filled with eitheran organic or an inorganic filler. Such fillers may be particulates,platelets, or fibers in either chopped or continuous form.

The uncrosslinked compositions may also be used as coatings, adhesives,or the feedstock for spinning fibers. Coatings of the uncrosslinkedcompositions of the present invention may be applied to a substrate byany of a number of methods, including, for example, dipping, brushing,spraying, and spin coating. Utility of these hybrid or ceramercompositions as coatings includes metal corrosion protection for saltwater and other salt environment conditions such as those encountered inmarine or automobile component use; for corrosive environments inindustrial applications such as in pump and engine components,pipelines, and tanks; for aerospace applications such as structuralcomposites and radome, for electrical insulation such as on wiring, forwaterproofing of surfaces such as fabric, concrete, and masonry, and formechanical protection of optical surfaces, wear surfaces, indoorflooring, and the like.

An artisan of ordinary skill in the art would understand that there areinnumerable uses for hybrid polymers or ceramers of the presentinvention. Presented below is a non-inclusive list demonstrating some ofthese innumerable uses. The list demonstrates that tailoring theproperties of the hybrid polymers or ceramers of the present inventionresults in engineerable material systems, and as such should be used asa guide. By no means should the list be construed as limiting, rather,the list is suggestive of the innumerable uses of the novel hybridpolymers or ceramers of the instant invention.

When the properties of the hybrid polymer or ceramer are tailored toinclude, for example, transparency, rigidity or stiffness, toughness orimpact resistance, abrasion resistance, weatherability or UV lightresistance and/or chemical resistance, the hybrid polymers or ceramersof the present invention would be ideally suited for use as, forexample, clear or colored transparent or translucent bodies including,for example, hard contact lenses, automotive lenses (e.g., headlights,taillights, etc.), safety and/or security glazing, skylights,illuminated signs, optical fibers, optical fiber coatings, windshields(e.g., automotive, construction equipment, motorcycles, etc.), guards(e.g., industrial machining equipment, commercial appliances, consumerappliances, etc.), mirrorized sheets, double extrusion panels (e.g.,solar energy applications, etc.), etc. Additionally, coatings possessingthe above listed properties may be used as, for example, floor waxes,emulsion or latex paints with increased temperature resistance withoutreducing transparency (e.g., baseball bats, fence posts, timbers, fencerails, decking, marine plywood, etc.). Additionally, the hybrid polymersor ceramers of the present invention may be applied as cements (e.g.,glues, contact adhesives, etc.) possessing properties for combiningchemically and/or microstructurally and/or structurally similar, ordissimilar materials including, for example, metals, minerals, ceramics(e.g., dental adhesives, ceramic paper, etc.), plastics or polymers,natural materials (e.g., to form plywood, particle board, etc.), metalmatrix composites, ceramic matrix composites, plastic or polymer matrixcomposites and combinations thereof.

Moreover, when the properties of the hybrid polymers or ceramers of thepresent invention are tailored to produce network polymers that form,for example, gels having good oxygen permeability uses may include, forexample, soft contact lenses, materials for gel chromatography,membranes, and the like.

Moreover, polymer alloys (polyalloys) or blends of the hybrid polymersor ceramers of the present invention may be used as, for example, rigidpipes or fittings for the construction industry, thermoformed liners(e.g., for refrigerator doors), small boat hulls, telephone machinehousings, business machine housings (e.g., typewriters, facsimilemachines, printers, monitors, computers, etc.), etc.

Moreover, when the properties of the hybrid polymer or ceramer of thepresent invention are tailored to include, for example, toughness orimpact resistance, water repellency, good surface appearance, oilresistance, fat resistance, grease resistance and optical clarity, usesmay include, for example, photographic films, transparency sheets,blister packaging, outdoor signs, metallized decorative parts, filmpackaging for the food industry (e.g., boil-in or bake-in bags orpouches, etc.), etc.

Moreover, when the properties of the hybrid polymers or ceramers of thepresent invention are tailored to include, for example, fatigueresistance, creep resistance, toughness or impact resistance, excellentfrictional or self-lubrication properties, wear resistance, abrasionresistance, chemical resistance, weatherability or UV light resistance,and flame resistance, any of a number of uses exist. For example, ahybrid polymer or ceramer of the present invention possessing goodmechanical and frictional or self-lubricating properties may be used,for example, as slides, guides or gear trains in mechanical or chemicalprocessing equipment, bearings, valves, impellots, propellors, housings(e.g., for portable appliances including circular saws, power drills,sanders, miter saws and the like). When the properties of the hybridpolymers or ceramers include hydrocarbon resistance, uses may include,for example, tanks for gas or chemicals exhibiting activity similar togas, automotive tubing or lines, etc.

Moreover, when the properties of the hybrid polymers or ceramers of theinstant invention are tailored to include, for example, good resistanceto oxygen permeation, as well as resistance to oils and greases, usesmay include, for example, film packaging for food (e.g., dairy products,meat products, etc.). Since the properties of the hybrid polymers orceramers of the present invention include temperature resistance, thefilm packaging for food may be used as, for example, boil-in or bake-inbags or pouches.

When the properties of the hybrid polymer or ceramer of the presentinvention are tailored to include, for example, temperature resistance,flame resistance and electrical insulation properties, uses mightinclude, for example, paper-like sheet as electrical insulation (e.g.,for transformers, electrical motors, generators, alternators, etc.).Furthermore, temperature resistant, flame resistant hybrid polymers orceramers may be used as, for example, protective fabric or clothing(e.g., gloves, jackets, leggings, aprons, head gear, etc.), conveyorbelts, textile fibers as tire cords, ropes, cables, coating fabric forinflatable structures, etc.

When the hybrid polymers or ceramers of the present invention are usedas matrices in filler reinforced composite materials, uses may include,for example, ballistic protection (e.g., vests, jackets, helmets, armorplates, composite armor systems, etc.), sporting equipment (e.g., skis,tennis rackets, fishing rods, ski boots, roller skate boots, in-lineskate boots, hockey skate boots, hockey skate blade supports, etc.),high performance marine structures (e.g., boat hulls, boat masts, etc.),high performance aerospace applications (e.g., satellitesuperstructures, solar panel supports, satellite armor, etc.).Furthermore, since the hybrid polymers or ceramers of the presentinvention exhibit heat resistance or reduced flammability, uses mayinclude, for example, applications such as brake linings (e.g.,automotive, aerospace, industrial, etc.), gaskets (e.g., automotive,chemical processing, etc.), packing, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are formed as film or sheets which may be biaxially oriented,uses may include, for example, photographic film, x-ray film, magnetictapes, electrical insulation, drafting sheets, food packaging bags(e.g., boil-in bags, retort pouches, etc.), etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, friction resistance,wear resistance, electrical insulation properties, low water absorption,low thermal expansion and chemical resistance, uses may include, forexample, electrical connectors, electrical fuse boxes, electrical coilbobbins, motor housings, brush holders, distributor caps, ignition coilcaps, automotive body panels, exterior mirror housings, power toolhousings, cookware handles, pump or meter housings, rotors, valves,motion-transmitting gears, windshield wiper frames, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, heat resistance, steamresistance, radiation resistance, weatherability or UV light resistance,and fire resistance, uses may include, for example, high performanceoutdoor transparent parts, microwave cookware, electrical or electronicparts, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, toughness or impactresistance, creep resistance, dimensional stability, low moistureabsorbance, self-extinguishing characteristics, non-flammability,chemical resistance, weatherability or UV light radiation resistance,uses may include any of a number of applications. When the propertiesare tailored to further include transparency, the uses may include, forexample, safety glazing for public places, windshield guards, streetlighting globes, automotive lenses, mirrorized sheets, double extrusionsfor solar energy applications, etc. When the properties are tailored tofurther include non-toxicity and general biocompatibility, the uses mayinclude, for example, housewares and food industries (e.g., returnablemilk bottles, returnable water bottles, beer pitchers, microwave ovenwear, medical applications, etc.). Since the properties of the hybridpolymers or ceramers of the present invention may be tailored fortoughness or impact resistance and high temperature resistance, uses mayinclude, for example, power tool housings, portable appliance housings,propellors, automotive applications, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include tolerance stability, dimensionstability, toughness or impact resistance and electrical insulatingproperties, uses may include, for example, camera bodies, modular phoneconnectors, compacitor films, ski slalom poles, drafting films, outboardmotor propellors, vacuum cleaner motor housings, electrical transformerbobbins, flat cable terminals, consumer and commercial applianceswitches and terminal plates, column packing for the chemical processingindustry, fiber optic couplers, microchip carriers, faceshields, helmetsand windshields for motorcycles, sunglasses, shrouded plugs and socketsin electrical applications, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, temperature resistant,stiffness, chemical resistance to ionizing radiation, fire resistance,creep resistance, low friction, wear resistance, electrical insulatingproperties, uses may include, for example, unlubricated bearings,bushings, thrust washers, piston rings, gears, ball-bearing cages orretainers, valve seats, gaskets, compressor vanes, turbine vanes, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, temperature resistanceand adhesion, uses may include, for example, binders (e.g., sandpaper,diamond tipped tooling, abrasive wheels, etc.), matrices for composites(e.g., carbon-carbon composites, organic filled, ceramic filled, metalfilled, etc.), high temperature filled or unfilled coatings (e.g., forexhaust systems, boiler equipment, engines, flues, etc.), etc.Furthermore, when the properties are tailored to include a non-stickattribute, uses may include, for example, non-stick cooking utensils(e.g., frying pans, pots, spatulas, etc.), mold release coatings, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, high temperatureelectrical resistance, uses may include, for example, wire or cableinsulation and/or coatings, solder resistant printed circuit boards,encapsulation or potting compounds for integrated circuits, filters,temperature and flame resistant fabrics, etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, a low dissipationfactor, and high dielectric strength, uses might include, for example,microwave applications, and the like.

When the hybrid polymers or ceramers of the present invention are usedas matrices and their properties are tailored to include, for example,good adhesion to the filler, high corrosion resistance and chemicalresistance, uses may include, for example, chemical processing equipment(e.g., piping, tanks, coatings, etc.), automotive (e.g., body panels,engine components, wheels, etc.), etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, thermal stability andchemical or corrosion resistance, uses may include, for example, bodiesin tough marine environments, protective coatings (e.g., industrial,architectural such as stone preservatives and build facia preservative,marine, etc.), linings (e.g., piping, tanks, drums and cans, etc.), etc.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, low loss factor and lowdielectric constant uses may include application requiring transparencyto radar such as, for example, radomes, aircraft leading edges, etc.Furthermore, when the hybrid polymers or ceramers possessing the abovetailored properties are used in combination with, for example, materialsuch as filler having high loss factors, uses may include lowobservables or stealth, shielding, and the like.

When the properties of the hybrid polymers or ceramers of the presentinvention are tailored to include, for example, electrical or electroniccompatibility, uses may include, for example, encapsulation or pottingmaterials for small components, laminated printed circuit boards,integrated circuits, large outdoor insulators, etc.

Since the properties of hybrid polymer or ceramers of the presentinvention inherently possess high temperature resistance, use requiringhigh temperature stability may be benefited from their uses. Somedesirable characteristics include extended thermal stability and highthermal char yield relative to their wholly organic counterparts. Forexample, the thermal characteristics of a standard Bisphenol "A" epoxyformulation (Curve A of FIG. 1) comprising an amine hardener arecompared to a polyureasilazane-hardened Bisphenol "A" epoxy resin (CurveB of FIG. 1) are shown in FIG. 1 to demonstrate the marked improvementin both the onset of thermal degradation as well as the improved charyields obtained for a Bisphenol "A" epoxy resin when apoly(methylvinyl)ureasilazane (Polymer A of Examples) is used as thehardener and the composition is thermally crosslinked through freeradical-induced vinyl group crosslinking and further thermally-inducedcondensation crosslinking by elimination of hydrogen gas evolved fromSi--H groups in the poly(methylvinyl)ureasilazane. The effect is seen tobe synergistic; that is, the char yield obtained in thepolyureasilazane-hardened system is higher than expected using a simplerule of mixtures. In the system represented in FIG. 1, about 50 wt % ofthe poly(methylvinyl)ureasilazane is used to harden about 50 wt % of thediglycidyl ether of Bisphenol "A". Typically, thepoly(methylvinyl)ureasilazane used demonstrates about a 72 wt % charyield under the conditions shown, while the conventional amine-hardeneddigylcidyl ether of Bisphenol "A" has a char yield of about 14 wt %under the same conditions. Using a simple rule of mixtures, thecalculated char yield would thus be approximately 43 wt %. As can beseen from FIG. 1, the actual char yield exceeds 70 wt %. FIG. 2demonstrates the improved thermal behavior of a system comprising of athermally crosslinked poly(methylvinyl)ureasilazane-hardenedpolyisocyanate. In this example, the polyisocyanate used is preparedfrom the oligomerization of methylene diphenyldiisocyanate. Again, theonset of thermal degradation is observed at a higher temperature than aconventional polyol-hardened polyisocyanate, and the improved char yieldis observed to exceed that expected from using a simple rule ofmixtures. In this example, a mixture of 80 wt % polyisocyanate is curedwith 20 wt % of poly(methylvinyl)ureasilazane (Polymer A of Examples).

Other examples of use of the hybrid polymers or ceramers as matrices incomposite materials may include, for example, sandfilled industrialflooring, pressure pipes, pressure tanks, motor casings, aerospacestructural components, etc.

Since the properties of hybrid polymer or ceramer of the presentinvention may range from, for example, soft rubber to engineeringplastics, uses may include, for example, pump liners, pump impellots,gears, sprocket wheels, bushings, shock mounts, O-rings, seals, gaskets,solid tires, wheel covers, roller coverings in the printing industry,sporting boots (e.g., skiing, hockey, roller blade, etc.), conveyorbelts, chute liners, etc.

Since the hybrid polymers or ceramers of the present invention may beformed into, for example, artificial or synthetic fiber, uses mayinclude, for example, garment, sports wear, surgical hoses, etc.

Since hybrid polymers or ceramers of the present invention may be usedas filled or unfilled coatings or combinations of filled and unfilledcoatings, uses may include, for example, finishes, paints, lacquers,varnishes, outer coatings (e.g., effected in fluidized beds), corrosionprotection (e.g., metals or alloys), electrical insulation,waterproofing (e.g., in fabrics and concretes), mechanical protection(e.g., optical surfaces), etc.

Moreover, when the properties of the hybrid polymers or ceramers of thepresent invention are tailored to include, for example, adhesion rangingfrom flexible to rigid adhesion, uses may include, for example, sealantsuch as caulking compound, moisture membranes such as barrier films,flexible tank liners, roofing membranes, etc.

As has been demonstrated by the above list, the novel hybrid polymers orceramers of the present invention have unlimited utility as filled orunfilled articles, composite articles, coating, adhesives, etc. Uses forthe hybrid polymers or ceramers of the present invention should not belimited by the above recitation, but to the contrary, the aboverecitation provides a basis for expanding the innumerated uses to alimitless number of, for example, equivalent uses.

The entire subject matter of each of the documents cited in the"Detailed Description of the Invention" is specifically incorporatedherein by reference.

Various demonstrations of the present invention are included in theExamples immediately following. However, these Examples should beconsidered as being illustrative and should not be construed as limitingthe scope of the invention as defined in the appended claims.

EXAMPLE 1

The present Example demonstrates, among other things, the preparation ofa polysilazane: [(CH₃ SiHNH)₀.8 (CH₃ Si(CH═CH₂)NH)₀.2 ]_(x). An about 5liter, three-necked flask was equipped with an overhead mechanicalstirrer, a dry ice/acetone condenser (about -78° C.), an ammonia ornitrogen inlet tube and a thermometer to form an apparatus. The interiorof the apparatus was sparged with nitrogen. The apparatus was thencharged with hexane (about 1760 milliliters (ml), dried over Type 4Amolecular sieves), methyldichlorosilane (about 209 ml, about 230.9 g,about 2.0 mol) and vinylmethyldichlorosilane (about 64 ml, about 69.6g., about 0.5 mol). Ammonia was added to the apparatus at a rate ofabout 3.5 liters per minute (about 9.37 mol) for about one hour. Duringthe ammonia addition, the temperature of the contents of the apparatusrose from about 25° C. to about 69° C. After about one hour, the ammoniaflow was stopped and the reaction mixture was allowed to cool to aboutroom temperature. The reaction mixture was filtered on a glass-frittedfunnel to remove any precipitated ammonium chloride. The hexane wasremoved from the filtrate under reduced pressure of about 2 millimeter(mm) mercury (Hg) (0.079 inch Hg) to give a product, polysilazane [(CH₃SiHNH)₀.8 (CH₂ ═CHSiCH₃ NH)₀.2 ]_(x), as a clear oil (about 150.8 gram(g), about 2.34 mol, about 94% yield) having a viscosity of about 43centipoise (cp) at about 25° C., and a molecular weight of about 560g/mol.

EXAMPLE 2

The present Example demonstrates, among other things, the preparation ofa polyureasilazane. A methylvinylpolyureasilazane was preparedsubstantially by the method of U.S. Pat. No. 4,929,704. That is, anabout 100 milliliter (ml) one-necked flask equipped with a stir bar anda septum was sparged with nitrogen and charged with about 10.0 g of thepolysilazane, [(CH₃ SiHNH)₀.8 (CH₃ Si(CH═CH₂)NH)₀.2 ]_(x), preparedsubstantially as described in Example 1 and about 0.2 wt % phenylisocyanate. The flask was placed in an oil bath on a stirrer/hot plateand the septum was replaced with a water condenser capped with a septum.A nitrogen inlet and oil bubbler outlet were placed in the septum. Thereaction mixture was then heated to about 110° C. under a nitrogenatmosphere for about 17 hours. Evolution of hydrogen gas was observed.After cooling to about room temperature, the viscosity of the liquidpolyureasilazane product measured about 300 centipoise.

EXAMPLE 3

The present Example demonstrates, among other things, the preparation ofa polyalazane:

{[(CH₃ CH₂)NAl(C₄ H₉)]_(y) [(CH₃ CH₂)NAl(C₄ H₇)]_(z) }n. A polyalazanewas prepared substantially by the method of U.S. Pat. No. 5,276,105.That is, about 250 ml round bottom flask was fitted with apressure-equalized dropping addition funnel and purged with nitrogen.Acetonitrile (about 50 ml, about 946 millimole (mmol)) was added to theflask. The funnel was charged with diisobutylaluminum hydride (about 100ml, about 1.0M in toluene, about 100 mmol) and the flask was cooled toabout 0° C. The diisobutylaluminum hydride was added dropwise over aperiod of about thirty minutes and stirred while maintaining atemperature of about 0° C. for about an additional hour. The flask waswarmed to about room temperature and the solution was stirredapproximately overnight. The solvent was removed under a vacuum, leavingabout 18 g of the yellow, liquid aluminum imine, [CH₃ C(H)═N--Al(i-C₄H₉)₂ ]₂.

A polyalazane was prepared by heating the about 5.0 g of aluminum imineat about 180° C. to about 200° C. for about 8 hours. Isobutene andisobutane evolved during the polymerization. The yield of polymer wasabout 3.5 g. The viscosity of the liquid polymer was about 52,000centipoise at about 30° C. measured using a Brookfield cone and plateviscometer.

EXAMPLE 4

The present Example demonstrates, among other things, the preparation ofa polyborazine. A polyborazine was prepared substantially by the methodof R. J. Brotherton and H. Steinberg, J. Org. Chem., Vol 26, 4632(1961). The borazine was prepared by heating a mixture of about 40.09 g(about 0.213 mole) of triisopropoxyborane and about 23.05 g (about 0.213mole) of o-phenylenediamine for about 18 hours in about 100 ml ofrefluxing xylene. The reaction mixture temperature rose as isopropylalcohol was removed by slow fractional distillation. After cooling toabout room temperature, the residual crude solid product was separatedby filtration and recrystallized from acetone to give about 6.19 g of5H,12H,19H-tris[1,3,2-benzodiazaborolo]borazine.

EXAMPLE 5

The present Example demonstrates, among other things, the preparation ofa silicon-nitrogen/aluminum-nitrogen, block copolymer. A block copolymerwas prepared substantially by the method of U.S. Pat. No. 5,229,468.That is, the block copolymer was prepared by combining about 15 grams ofthe polysilazane, [(CH₃ SiHNH)₀.8 (CH₃ Si(CH═CH₂)NH)0.2]_(x), preparedsubstantially as described in Example 1, and about 5 grams of thepolyalazane, {[(CH₃ CH₂)NAl(C₄ H₇)(C₄ H₉)]_(y) [(CH₃ CH₂)NAl(C₄ H₇)]_(z)}n, prepared substantially as described in Example 3, and heating undernitrogen to about 110° C. for about 5 hours. Isobutane was formed as aby-product of the reaction. The resulting poly(silazane/alazane) blockcopolymer comprised an orange liquid.

The following designations are used (or the metal-nitrogen polymers inthe remaining examples:

Polymer A--Poly(methylvinyl)silazane (made substantially according tothe method of Example 1)

Polymer B--Poly(methylvinyl)ureasilazane (made substantially accordingto the method of Example 2, CERASET® SN preceramic polymer, LanxideCorp., Newark, Del.)

Polymer C--Hexamethylcyclotrisilazane (Huls Petrach Systems, Bristol,Pa.)

Polymer D--Polyalazane (made substantially according to the method ofExample 3)

Polymer E--Polyborazine (made substantially according to the method ofExample 4)

Polymer F--Poly(silazane/alazane) block copolymer (made substantiallyaccording to the method of Example 5)

EXAMPLES 6-17

The present Examples demonstrate, among other things, the formation ofreacted compositions made from mixtures comprising ap,p'-diphenylmethane diisocyanate--based resin (an aromaticdiisocyanate) and a metal-nitrogen polymer. Table I sets forth forExamples 6-17 (Ex.) the metal-nitrogen polymer (Inorganic Polymer), thetime to cure (Time), the various component ratios of (Isocyanate levelin wt %) Part "A" of a urethane casting resin (Smooth-On™ C-1506 RigidUrethane Casting Resin; Smooth-On, Inc., 1000 Valley Road, Gillette,N.J.) at about the specified temperatures (Temp.). Table I also setsforth the form (Form) of the cured reacted composition. The mixturessummarized in Table I initially reacted to form viscous liquidcompositions before curing to the composition having the described form.

                                      TABLE I                                     __________________________________________________________________________    Compositions Made From Mixtures Comprising Isocyanate and a                   Metal-Nitrogen Polymer                                                        Inorganic Isocyanate                                                                          Temp.            Isocyanate                                                                          Temp.                                  Polymer   Level (°C.)                                                                      Time Form    Level (°C.)                                                                      Time Form                          __________________________________________________________________________    Polymer A                                                                           Ex 6:                                                                             75 wt %                                                                             25  10                                                                              min                                                                              Solid                                                                             Ex 7:                                                                             50 wt %                                                                             100 20                                                                              min                                                                              Solid                         Polymer B                                                                           Ex 8:                                                                             75 wt %                                                                             25  5 min                                                                              Solid                                                                             Ex 9:                                                                             50 wt %                                                                             100 20                                                                              min                                                                              Solid                         Polymer C                                                                           Ex 10:                                                                            75 wt %                                                                             25  5 min                                                                              Solid                                                                             Ex 11:                                                                            50 wt %                                                                              25 15                                                                              min                                                                              Solid                         Polymer D                                                                           Ex 12:                                                                            75 wt %                                                                             120 1 hr Gel Ex 13:                                                                            50 wt %                                                                             120 1 hr Solid                         Polymer E                                                                           Ex 14:                                                                            75 wt %                                                                             250 1 hr Solid                                                                             Ex 15:                                                                            50 wt %                                                                             250 1 hr Solid                         Polymer F                                                                           Ex 16:                                                                            75 wt %                                                                             25  1 hr Gel Ex 17:                                                                            50 wt %                                                                              25 1 hr Solid                         __________________________________________________________________________

EXAMPLES 18-29

The present Examples demonstrate, among other things, the formation ofliquid compositions made from mixtures comprising hexamethylenediisocyanate (an aliphatic diisocyanate) and a metal-nitrogen polymer.Table II sets forth for Examples 18-29 the metal-nitrogen polymer(Inorganic Polymer), the time to cure (Time), the various componentratios (Isocyanate level in wt %) of hexamethylene diisocyanate (Cat.No. D12,470-2, Aldrich Chemical Company, Inc., Milwaukee, Wis.) at aboutthe specified temperatures (Temp.). Table II also sets forth the form ofthe cured reacted composition. The mixtures summarized in Table IIinitially reacted to form viscous liquid compositions before curing tothe composition having the described form.

                                      TABLE II                                    __________________________________________________________________________    Compositions Made From Mixtures Comprising Isocyanates and a                  Metal-Nitrogen Polymer                                                        Inorganic Isocyanate                                                                          Temp.             Isocyanate                                                                          Temp.                                 Polymer   Level (°C.)                                                                      Time Form     Level (°C.)                                                                      Time Form                         __________________________________________________________________________    Polymer A                                                                           Ex 18:                                                                            75 wt %                                                                             100 2 hr Liquid                                                                             Ex 19:                                                                            50 wt %                                                                             100 25                                                                              min                                                                              Solid                                        100 3 hr Rubber                                               Polymer B                                                                           Ex 20:                                                                            75 wt %                                                                             100 30                                                                              min                                                                              Liquid                                                                             Ex 21:                                                                            50 wt %                                                                             100 15                                                                              min                                                                              Solid                                        100 1 hr Rubber                                               Polymer C                                                                           Ex 22:                                                                            75 wt %                                                                             100 2 hr Liquid                                                                             Ex 23:                                                                            50 wt %                                                                              25 20                                                                              min                                                                              Rubber                                       100 3 hr Gel                                                  Polymer D                                                                           Ex 24:                                                                            75 wt %                                                                             100 1 hr Solid                                                                              Ex 25:                                                                            50 wt %                                                                             120 10                                                                              min                                                                              Solid                        Polymer E                                                                           Ex 26:                                                                            75 wt %                                                                             250 12                                                                              hr No Cure                                                                            Ex 27:                                                                            50 wt %                                                                             250 12                                                                              hr No Cure                      Polymer F                                                                           Ex 28:                                                                            75 wt %                                                                             120 1 hr Solid                                                                              Ex 29:                                                                            50 wt %                                                                             120 15                                                                              min                                                                              Solid                        __________________________________________________________________________

EXAMPLE 30

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising isocyanate and polyureasilazanecomposition comprising a peroxide free radical initiator. An about 1.0wt % DI-CUP® R dicumyl peroxide (Hercules Inc., Wilmington, Del.) basedon the combined weight of metal-nitrogen polymer and the diisocyanatewas added to a composition made substantially according to the method ofExample 8. The liquid mixture first reacted to form a viscous liquidcomposition, and cured to a solid composition after at about 100° C. forabout 3 minutes.

EXAMPLE 31

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising an isocyanate and polyureasilazanefurther comprising an azo compound as free radical initiator. A mixturecomprising about 1.0 wt % azoisobutyronitrile (AIBN) (Stk. No. 36307,ALFA® AESAR®, Johnson Matthey, Ward Hill, Mass.) based on the combinedweight of the metal-nitrogen polymer and the diisocyanate was added to amixture made substantially according to the method of Example 9. Theliquid mixture cured to a rigid, solid composition after at about 100°C. for about 5 minutes.

EXAMPLES 32-35

The present Examples demonstrate, among other things, the formation ofliquid compositions from mixtures comprising hexamethylene diisocyanate(aliphatic diisocyanates) and a metal-nitrogen polymer furthercomprising phthalic acid (PA) (Cat. No. 40,291-5, Aldrich ChemicalCompany, Inc., Milwaukee, Wis.) as the isocyanate cure catalyst. TableIII sets forth for Examples 32-35 the metal-nitrogen polymer (InorganicPolymer), the time (Time) to cure at various component ratios (wt %) atabout room temperature and the form (Form) of the resultingcompositions.

                                      TABLE III                                   __________________________________________________________________________    Liquid Compositions Made From Mixtures Comprising Diisocyanates and a         Metal-Nitrogen                                                                Polymer                                                                                     Diisocyanate (wt %) Level:                                                    75 wt %          50 wt %                                                      Temp.            Temp.                                          Inorganic Polymer                                                                           (°C.)                                                                      Time Form    (°C.)                                                                      Time                                                                              Form                                   __________________________________________________________________________    Polymer A: with 10 wt % Phthalic Acid                                                   Ex 32:                                                                            100 2 min                                                                              Solid                                                                             Ex 33:                                                                            80  30 min                                                                            Solid                                                 80 1 hr Solid                                                  Polymer B: with 10 wt % Phthalic Acid                                                   Ex 34:                                                                            100 2 min                                                                              Solid                                                                             Ex 35:                                                                            80  30 min                                                                            Solid                                                 80 1 hr Solid                                                  __________________________________________________________________________

EXAMPLE 36

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising a polyureasilazane and adiisocyanate. An uncured, liquid mixture was prepared in an open vesselby mixing about 350 grams of an isocyanate component used in Example 8and about 87 grams of Polymer B (in which about 0.5 wt % DI-CUP® Rdicumyl peroxide, Hercules Inc., Wilmington, Del., had been added)cooled to about 2° C. The mixture was poured into a cavity of analuminum mold. After hardening at about room temperature, the moldedmixture was heated at about 110° C. for about 4 hours. A rigid, solidcomposition substantially replicating the shape of the cavity ofaluminum mold was formed. Mechanical properties testing (measuresubstantially as described in Example 76) of tensile bars cut from therigid, solid, molded composition had a tensile modulus of about 1.8 GPaand a tensile strength of about 14 MPa.

EXAMPLE 37

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising a polyureasilazane and adiisocyanate and further comprising ceramic filler. About 120 grams ofabout 1,000 grit (average particle diameter of about 5 microns) boroncarbide (B₄ C) (Elektroschmelzwerk, Kempton (ESK), Germany) were admixedwith about 180 grams of the isocyanate component used in Example 8 andabout 42 grams of the Polymer B (in which about 0.5 wt % DI-CUP® Rdicumyl peroxide, Hercules Inc., Wilmington, Del., had been added). Themixture was poured into a cavity of an aluminum mold. The mixture wasallowed to cure to a rigid, solid composition which substantiallyreplicated the shape of the cavity of the aluminum mold. Mechanicalproperties testing (measure substantially as described in Example 76) oftensile bars cut from the rigid, solid composition had a tensile modulusof about 6.2 GPa and a tensile strength of about 33 MPa.

EXAMPLE 38

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising a polyureasilazane and adiisocyanate and further comprising a metal filler. About 10 grams ofaluminum powder flake (UN1396, Grade 7100, Alcan Powders and Chemicals,Elizabeth, N.J.) were admixed with about 45 grams of Part "A" of aurethane casting resin (Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.) and about 9 grams ofthe Polymer B (to which about 0.5 wt % DI-CUP® R dicumyl peroxide,Hercules Inc., Wilmington, Del., had been added) in an open vessel andpoured into a cavity of a rubber mold. The molding mixture curedovernight to a rigid, solid composition which substantially replicatedthe shape of the cavity of the rubber mold.

EXAMPLE 39

The present Example demonstrates, among other things, the formation bysolution polymerization of a composition from a mixture comprising apolyureasilazane and a diisocyanate. About 10 grams of Polymer B werestirred with about 40 ml of dry hexane (dried over 13× molecular sieve,Cat. No. 29,325-3, Sigma-Aldrich, Sigma Chemical Co., St. Louis, Mo.) atabout room temperature under a nitrogen atmosphere. About 10 grams ofhexamethylene diisocyanate (Cat. No. D12, 470-2, Aldrich ChemicalCompany, Inc., Milwaukee, Wis.) were then added to the reaction mixture.A fine white haze formed within the reaction mixture and became morenoticeable with time. The reaction mixture was then heated to reflux. Asthe solution was heated, the fine haze (suspended precipitate)disappeared. After about 15 minutes at a heavy reflux, white precipitateformed. The reaction was continued for about an additional hour atreflux. On cooling, the solid precipitate was removed from solution bydecanting the hexane solvent. The solid, polymeric composition wasinsoluble in hot toluene.

EXAMPLES 40-53

The present Examples demonstrate, among other things, the formation ofliquid compositions from mixtures comprising the diglycidyl ether ofBisphenol "A" (an aromatic diepoxide) (Cat. No. 8760, DajacLaboratories, Inc., Southhampton, Pa.) and a metal-nitrogen polymer.Table IV sets forth for Example 40-53 the metal-nitrogen polymer(Inorganic Polymer), the time (Time) to cure at various component ratios(Level in wt %) of the diglycidyl ether of Bisphenol "A" (Cat. No. 8760,Dajac Laboratories, Inc., Southhamptom, Pa.) at various specifiedtemperatures (Temp.). Table IV also sets forth the form (Form) of thecured reacted composition. The mixtures set forth in Table IV initiallyreacted to form viscous liquid compositions before curing to thecompositions of the described form. The mixtures in Table IV comprisingPolymers A, B, and C further comprised about 5 wt % of DI-CUP® R dicumylperoxide (Hercules Inc., Wilmington, Del.) free radical generator.

                                      TABLE IV                                    __________________________________________________________________________    Liquid Compositions Made From Mixtures Comprising Diepoxides and a            Metal-Nitrogen Polymer                                                        Inorganic       Temp.                Temp.                                    Polymer   Diepoxide                                                                           (°C.)                                                                      Time                                                                             Form    Diepoxide                                                                           (°C.)                                                                      Time                                                                             Form                              __________________________________________________________________________    Polymer A                                                                           Ex 40:                                                                            75 wt %                                                                             120  2 hr                                                                            Gel Ex 41:                                                                            50 wt %                                                                             120  2 hr                                                                            Solid                             Polymer B                                                                           Ex 42:                                                                            75 wt %                                                                             120  2 hr                                                                            Gel Ex 43:                                                                            50 wt %                                                                             120  2 hr                                                                            Solid                             Polymer C                                                                           Ex 44:                                                                            75 wt %                                                                             150 12 hr                                                                            Rubber                                                                            Ex 45:                                                                            50 wt %                                                                             150 12 hr                                                                            Gel                               Polymer D                                                                           Ex 46:                                                                            75 wt %                                                                             130 12 hr                                                                            Solid                                                                             Ex 47:                                                                            50 wt %                                                                             130 12 hr                                                                            Solid                             Polymer E                                                                           Ex 48:                                                                            75 wt %                                                                             250  1 hr                                                                            Solid                                                                             Ex 49:                                                                            50 wt %                                                                             250  1 hr                                                                            Solid                             Polymer F                                                                           Ex 50:                                                                            75 wt %                                                                             100 12 hr                                                                            Solid                                                                             Ex 51:                                                                            50 wt %                                                                             100 12 hr                                                                            Solid                             __________________________________________________________________________

EXAMPLE 52

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising diepoxide and a polyureasilazanefurther comprising an azo compound as free radical initiator. About 1.0wt % azoisobutyronitrile (AIBN) (Stk. No. 36307, ALFA® AESAR®, JohnsonMatthey, Ward Hill, Mass.) based on the combined weight of Polymer A andthe diepoxide was added to a mixture made substantially according to themethod of Example 43. The liquid mixture cured to a rigid, solidcomposition in about 20 minutes.

EXAMPLE 53

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising a diepoxide and a polyureasilazanefurther comprising an epoxy cure catalyst. About 5% by weight ofTi(O^(i) Pr)₄ (Cat. No. 20,527-3, titanium (IV) isopropoxide, AldrichChemical Company, Inc., Milwaukee, Wis.) was added to a mixture madesubstantially according to the methods of Example 43. The mixture curedto a rigid, solid composition after at about 120° C. for about 30minutes.

EXAMPLE 54

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising a polyureasilazane and adiepoxide. A mixture made substantially according to the method ofExample 43 was handmixed in an open vessel. The mixture was poured intoa cavity of an aluminum mold. The molded mixture was cured substantiallyas in Example 43. The demolded composition substantially replicated theshape of the cavity of the aluminum mold.

EXAMPLE 55

The present Example demonstrates, among other things, the formation of acomposition comprising a polyureasilazane and a diepoxide and furthercomprising ceramic filler. A mixture made substantially according to themethods of Example 43 and about 50 wt %, 180 grit (average particlediameter of about 86 microns) boron carbide (B₄ C) (Elektroschmelzwerk,Kempton (ESK), Germany) powder were combined in an open vessel, mixedand poured into a cavity of an aluminum mold. The molded mixture wascured substantially as in Example 43. The demolded compositionsubstantially replicated the shape of the cavity of the aluminum mold.

EXAMPLE 56

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising a polyureasilazane and a diepoxideand further comprising metal filler. A mixture made substantiallyaccording to the methods of Example 43 and about 50 wt %, -325 mesh(average particle diameter less than about 45 microns) iron metal powder(Alfa Catalog Chemicals, Morton Thiokol, Inc., Danvers, Mass.) werecombined in an open vessel, mixed and poured into a cavity of analuminum mold. The molded mixture was cured substantially as in Example43. The demolded composition substantially replicated the shape of thecavity of the aluminum mold.

EXAMPLE 57

The present Example demonstrates, among other things, the formation bysolution polymerization of a composition from a mixture comprising apolyureasilazane and a diepoxide. About 10 grams of the diglycidyl etherof Bisphenol "A" (Cat. No. 8760, Dajac Laboratories, Inc., Southhamptom,Pa.) were dissolved in about 40 mls of dry toluene (dried over 13×molecular sieve, Cat. No. 17,996-5, Aldrich Chemical Company, Inc.,Milwaukee, Wis.). About 10 grams of polyureasilazane (Polymer B) werethen added to the toluene solution and the solution was stirred whilerefluxing for about 18 hours. Gas bubbles formed during heating to thereflux temperature. After about 18 hours at reflux the reaction solutionwas cooled to about room temperature and the toluene solvent wasremoved. A viscous, colorless liquid composition was recovered.

EXAMPLES 58-63

The present Example demonstrates, among other things, the formation ofcomposition from mixtures which were prepared by dissolving about 0.5grams of polybutylmethacrylate polymer (ELVACITE® 2045 acrylic binder,Dupont Chemicals, Wilmington, Del.) in about 1.0 grams of toluene (Cat.No. 17,996-5, Aldrich Chemical Company, Inc., Milwaukee, Wis.) followedby an addition of about 1.25 grams of a metal-nitrogen polymer as shownin Table V. The solutions were cast as a film onto stainless steelplates and heated to effect cure to a rigid, solid, coating compositionon the plates. Table V sets forth for Examples 58-63 the metal-nitrogenpolymer (Inorganic Polymer), the specified time (Time) to cure atvarious component ratios (wt %) at the specified temperatures (Temp.)and the resulting form (Form) of the coating composition.

                  TABLE V                                                         ______________________________________                                        Compositions Made from Mixtures Comprising                                    Butylmethacrylates and a Metal-Nitrogen Polymer                               Inorganic                                                                     Polymer Polybutyl-                                                            (60 wt %                                                                              methacrylate                                                          Ratio)  (40 wt % Ratio)                                                                           Temp.    Cure Time                                                                             Form                                     ______________________________________                                        Polymer A                                                                             Ex 58:      100° C.                                                                         10 min  Clear Coat                               Polymer B                                                                             Ex 59:      100° C.                                                                         10 min  Clear Coat                               Polymer C                                                                             Ex 60:      100° C.                                                                          5 min  Clear Coat                               Polymer D                                                                             Ex 61:      100° C.                                                                          5 min  Hazy Coat                                Polymer E                                                                             Ex 62:      150° C.                                                                         30 min  Hazy Coat                                Polymer F                                                                             Ex 63:      100° C.                                                                         10 min  Hazy Coat                                ______________________________________                                    

EXAMPLE 64

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising a polyureasilazane and apolybutylmethacrylate. A liquid mixture was prepared by combining about75 grams of a polyureasilazane prepared substantially according to themethod of Example 2 with about 1.5 grams of DI-CUP® R dicumyl peroxide(Hercules Inc., Wilmington, Del.), about 50 grams ofpolybutylmethacrylate (ELVACITE® 2045 acrylic binder, DuPont Company,Wilmington, Del.) and about 325 grams of xylene (Cat. No. 24,764-2,Aldrich Chemical Company, Inc., Milwaukee, Wis.). A large aluminum part(which was first surface treated by sandblasting) was coated with themixture by dipping and draining the dipped part at about 5 minutes. Thecoating mixture was cured by heating the dip coated part at about 150°C. for about 12 hours. A clear, colorless, coating composition resulted.The coating composition exhibited hardness and abrasion resistant.Coating composition adhesion was also excellent.

EXAMPLE 65

The present Example demonstrates, among other things, the formation ofcompositions from a mixture comprising a polyuresilazane and apolybutylmethacrylate. The method of Example 64 was substantiallyrepeated, except that instead of dipping, the liquid mixture waspour-coated. The resulting coating composition was quite hard andabrasion resistant. Coating composition adhesion was excellent.

EXAMPLE 66

The present Example demonstrates, among other things, the formation ofcomposition from a mixture comprising a polyureasilazane and apolybutylmethacrylate. A liquid mixture was prepared by combining about75 grams of the Polymer B (polyureasilazane prepared substantiallyaccording to the methods of Example 2) with about 1.5 grams of DI-CUP® Rdicumyl peroxide (Hercules Inc., Wilmington, Del.), about 50 grams ofpolybutylmethacrylate (ELVACITE® 2045 acrylic binder, DuPont Chemicals,Wilmington, Del.) and about 100 grams of xylene (Cat. No. 24,764-2,Aldrich Chemical Company, Inc., Milwaukee, Wis.). Ten steel pipesmeasuring about 14 inches (356 mm) long×2.5 inches (63.5 mm) outsidediameter×1/16 inches (1.6 mm) wall thickness were dip-coated and curedas described in Example 64. The resulting coating compositions weresmooth, quite hard and abrasion resistant. Coating compositions adhesionwas also excellent.

EXAMPLE 67

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising polybutylmethacrylate and ametal-nitrogen polymer. One part polybutylmethacrylate (ELVACITE® 2045acrylic binder, DuPont Company, Wilmington, Del.) was dissolved in abouttwo parts of xylene solvent (Cat. No. 24,764-2, Aldrich ChemicalCompany, Inc., Milwaukee, Wis.). About two parts of this solution werethen added to about one part of the polyureasilazane substantiallyprepared as in Example 2 (to which about 10 wt % of tert-butyl benzoylperoxide, ATOCHEM North America, Inc., Crosby, Tex., had been added).This mixture was allowed to stand under a laboratory hood to evaporatethe xylene solvent and then about 5 grams of the remaining mixture werecast into a cavity of an aluminum mold. The casting mixture was thenheated at about 110° C. for about 2 hours, resulting in a rigidcomposition which substantially replicated the shape of the cavity ofthe aluminum mold.

EXAMPLE 68

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising polybutylmethacrylate and ametal-nitrogen polymer and further comprising a glass fiber filler (S-2glass, Owens/Corning, Huntingdon, Pa.). About 20 grams of a solventlessmixture made substantially according to the methods of Example 67 werecast into a cavity of an aluminum mold containing 4 plies of 8 harnesssatin weave woven glass fiber mat. The molded mixture was heated atabout 110° C. for about 2 hours, resulting in a rigid, glass fiberreinforced composition which substantially replicated the shape of thecavity of the aluminum mold.

EXAMPLE 69

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising polybutylmethacrylate and ametal-nitrogen polymer and further comprising metal filler. About 9grams of a solventless mixture made substantially according to themethods of Example 67 further comprising about 4 grams of -325 mesh(particle diameter less than about 45 microns) iron metal powder filler(Alfa Catalog Chemicals, Morton Thiokol, Inc., Danvers, Mass.) were castinto a cavity of an aluminum mold. The molded mixture was heated atabout 110° C. for about 2 hours, resulting in a rigid composition whichsubstantially replicated the shape of the cavity of the aluminum mold.

EXAMPLES 70-75

The present Examples demonstrate, among other things, the formation ofliquid compositions from mixtures comprising DBE-6 dimethyl adipate(Dupont Chemicals, Wilmington, Del.) and a metal-nitrogen polymer. TableVI summarizes the metal-nitrogen polymer (Inorganic Polymer), the timeto cure (Cure Time) at various component ratios of dimethyl adipate atvarious temperatures (Temp.) and the resulting form (Form) of theresulting composition for Examples 70-75. The mixtures comprisingPolymers A, B, and C further comprised about 5 wt % of DI-CUP® R dicumylperoxide (Hercules Inc., Wilmington, Del.) free radical generator.

                  TABLE VI                                                        ______________________________________                                        Liquid Compositions Made From Mixtures Comprising                             Adipates and Metal-Nitrogen Polymer                                           Inorganic                                                                     Polymer Dimethyl                                                              (25 wt %                                                                              Adipate     Temp.                                                     Ratio)  (75 wt % Ratio)                                                                           (°C.)                                                                           Cure Time                                                                             Form                                     ______________________________________                                        Polymer A                                                                             Ex 70:      120      2 hr    Solid                                    Polymer B                                                                             Ex 71:      120      2 hr    Solid                                    Polymer C                                                                             Ex 72:      150      12 hr   Liquid                                   Polymer D                                                                             Ex 73:      120      1 hr    Solid                                    (@ 50   (@ 50 wt %)                                                           wt %)                                                                         Polymer E                                                                             Ex 74:      250      12 hr   No Cure                                  Polymer F                                                                             Ex 75:      120      1 hr    Solid                                    ______________________________________                                    

EXAMPLE 76

The present Example demonstrates, among other things, the formation of acomposition from a mixture comprising diglycidyl ether of Bisphenol "A"and a metal-nitrogen polymer and further comprising carbon fiber filler.

A liquid solution was prepared by combining by weight about 1 percentphthalic acid (Cat. No. 40,291-5, Aldrich Chemical Company, Inc.,Milwaukee, Wis.) and about 99 percent diglycidyl ether of Bisphenol "A"(Cat. No. 8760, Dajac Laboratories, Inc., Southhamptom, Pa.). The liquidsolution was placed into a ceramic milling jar with about 1 inch (25.4mm) diameter alumina milling stones. The ratio by weight of the aluminamilling stones to the liquid solution was about 2:1. After the millingjar was closed, the jar and its contents were placed on a rolling millfor about 6 hours. The jar and its contents were then removed from therolling mill and the alumina milling stones were separated from theliquid solution. The liquid solution was then placed under a vacuum belljar and subjected to a vacuum of about 30 inches (762 mm) of mercury forabout 5 minutes.

A molding mixture was prepared by combining by weight about 50 percentof the liquid solution and about 50 percent Polymer B. After handmixing,the molding mixture which was contained within a plastic jar was placedon a rolling mill for about an hour. After removing from the rollingmill, the molding mixture was degassed using a vacuum bell jar at avacuum of about 30 inches (762 mm) of mercury for about 5 minutes. Themolding mixture was then poured into a pan having inner dimensionsmeasuring about 14 inches (356 mm) by about 12 inches (304.8) by about 2inches (50.8 mm).

A material composition was then prepared by following steps. Twelveplies of uniaxial carbon fiber (Grade AS4-G 3K, Hercules Inc.,Wilmington, Del.) measuring about 12 inches (304.8 mm) by about 5 inches(127 mm) were cut. Two steel platens measuring about 12 inch (304.8 mm)square by about 0.25 inch and machined to a flatness of about ±0.001inch (0.025 mm) thick were spray coated with a polyester-based parfilm(Price-Driscoll Corp., Farmingdale, N.Y.). The 12 inch (304.8 mm) squaresurface of one of the steel platens was covered with a piece of graphitesheet measuring about 12 inches (304.8 mm) square and about 0.005 inch(0.127 mm) thick (PERMAFOIL, TT America, Portland, Oreg.). Each of the12 uniaxial plies of the carbon fiber were individually dipped into themolding mixture contained within the baking pan. After each ply wassubstantially saturated by the molding mixture, the ply was removed fromthe molding mixture and excess molding mixture allowed to drip from theply. The first ply was placed in contact with the graphite foil sheet.This process was repeated with the remaining 11 plies and the remainingplys were stacked so that the carbon fibers of all the plies weresubstantially parallel with the fibers and the edges of the first ply. Asecond piece of graphite foil, measuring substantially the same as thefirst, was placed on top of the molding mixture saturated and alignedplies. The second steel platen was then placed on the second piece ofgraphite foil to compress the stack of plies. An additional weight ofabout 40 pounds (18.1 kilograms) was then placed on top of the secondsteel platen to form a curing lay-up.

The curing lay-up was placed in an oven and the molding mixturesaturating the 12 carbon fiber plies was cured at about 80° C. for about1 hour, then at about 120° C. for about 4 hours and then finally atabout 180° C. for 12 hours prior to cooling to about room temperature.At about room temperature, a material composition comprising uniaxiallyaligned carbon fibers was obtained.

The material composition was then prepared for tensile strength testing.Specifically, the tensile strength of the material compositionreinforced with the uniaxially carbon fibers was measured usingprocedures substantially as described in ASTM designation: D638-91(ASTM, Philadelphia, Pa.). Modified Type I tensile specimens weremachined using diamond grinding so that the longitudinal axis of thetest specimen was parallel to the uniaxial fibers of the materialcomposition. The tensile test specimens were machined from couponsmeasuring about 8 inches (203 mm) long, about 0.5 inches (12.7 mm) wideand about 0.12 inches (3 mm) thick. The gauged section of the tensiletest specimens measured about 1.25 inches (31.75 mm) long by about 0.35inches (9 mm) wide. About 3 inches (76 mm) radii were machined to createthe reducing transition from the tabbed portion of the tensile specimensinto the reduced gauge section.

Tensile strength of the material composition was measured as a functionof temperature. An INSTRON® Model 8501 servo hydraulic testing machine(Instron Corp., Canton, Mass.) (operated at a cross head speed of about0.0047 inch (0.12 mm) per minute in the elastic region of the materialcomposition). Tensile sample strain was monitored with an instron hightemperature capacitive extendsometer (Catalog No. 3118-231, InstronCorp. Canton, Mass.). The temperature of the specimens was controlledusing an Instron two-zone short furnace (Catalog No. 3118-220, InstronCorp. Canton, Mass.). Table VII sets forth the ultimate elastic modulus,the tensile strength and the strain rate used after the elastic orlinear region of the material composition for each tensile test specimenas a function of temperature. The test temperatures included roomtemperature, 150° C., 250° C., 350° C., 400° C., 450° C. and 600° C.

                  TABLE VII                                                       ______________________________________                                        Tensile Properties as a Function of Temperature                               for a Composition Comprising Carbon Fiber Filler                                                Ultimate                                                    Test     Elastic  Tensile  Sample Strain Rate                                 Temperature                                                                            Modulus  Strength to Failure and After Elastic                       °C.                                                                             (GPA)    (MPA)    Region inch (mm) per min.                          ______________________________________                                        Room     100      750      0.0047 (0.12)                                      Temperature                                                                   150      70       625      0.019 (0.5)                                        250      70       400      0.019 (0.5)                                        350      70       400      0.041 (1.0)                                        400      65       375      0.041 (1.0)                                        450      65       300      0.079 (2.0)                                        600      65       150      0.079 (2.0)                                        ______________________________________                                    

EXAMPLE 77

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyureasilazane and adiisocyanate. A molding mixture was prepared in an open vessel byhandmixing about 350 grams of Part "A" of a urethane casting resin(Smooth-On™ C-1506 Rigid Urethane Casting Resin; Smooth-On, Inc., 1000Valley Road, Gillette, N.J.) with about 87 grams of Polymer B (in whichabout 0.5 wt % DI-CUP® R dicumyl peroxide, Hercules Inc., Wilmington,Del., had been added). The liquid polureasilazane and the diisocyanatewere cooled to about 2° C. before handmixing. The molding mixture waspoured into a cavity of an aluminum mold. After the molding mixturehardened at about room temperature, the molded mixture was heated atabout 110° C. for about 4 hours. A rigid, solid molded composition whichsubstantially replicated the shape of the cavity of the aluminum moldwas obtained.

EXAMPLE 78

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyureasilazane and adiisocyanate and further comprising a ceramic filler. A molding mixturewas prepared in an open vessel by handmixing about 120 grams of 1,000grit (average particle diameter of about 5 microns) boron carbide (B₄C), about 180 grams of Part "A" of a urethane casting resin (Smooth-On™C-1506 Rigid Urethane Casting Resin; Smooth-On, Inc., 1000 Valley Road,Gillette, N.J.) and about 42 grams of Polymer B (in which about 0.5 wt %dicumyl peroxide had been added). The molding mixture was poured into acavity of an aluminum mold. The molding mixture was cured. A rigid,solid composition substantially replicating the shape of the cavity ofthe aluminum mold was obtained.

EXAMPLE 79

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyureasilazane and adiisocyanate and further comprising a metal filler. A molding mixturewas prepared in an open vessel by handmixing about 10 grams of aluminumpowder flake (UN1396, Grade 7100, Alcan Powders & Chemicals, Elizabeth,N.J.), about 45 grams of Part "A" of a urethane casting resin(Smooth-On™ C-1508 Rigid Urethane Casting Resin; Smooth-On, Inc., 1000Valley Road, Gillette, N.J.) and about 9 grams of Polymer B (to whichabout 0.5 wt % DI-CUP® R dicumyl peroxide, Hercules Inc., Wilmington,Del., had been added). The molding mixture was poured into a cavity of arubber mold. The molding mixture was allowed to cure at about roomtemperature overnight. A rigid, solid composition substantiallyreplicating the shape of the cavity of the rubber mold was obtained.

EXAMPLE 80

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyureasilazane and adiepoxide. A mixture was prepared by handmixing by weight about 50 partsof the diglycidyl ether of Bisphenol "A" (Cat. No. 8760, DajacLaboratories, Inc., Southhamptom, Pa.) with about 50 parts of Polymer Bin an open vessel. The molding mixture was then poured into a cavity ofan aluminum mold. The molded mixture was cured by heating at about 120°C. for about 2 hours. A composition substantially replicating the shapeof the cavity of the aluminum mold was obtained.

EXAMPLE 81

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyureasilazane and adiepoxide and further comprising a ceramic filler. A molding mixture wasprepared by handmixing by weight about 50 parts of the diglycidyl etherof Bisphenol "A" (Cat. No. 8760, Dajac Laboratories, Inc., Southhamptom,Pa.) with about 50 parts of Polymer B in an open vessel. About 50 wt %,180 grit (average particle diameter of about 86 microns) boron carbide(B₄ C) (Elektroschmelzwerk, Kempton (ESK), Germany) powder was added toand handmixed into the molding mixture in the open vessel. The moldingmixture comprising the filler was then poured into a cavity of analuminum mold. The molded mixture was cured by heating at about 120° C.for about 2 hours. A composition substantially replicating the shape ofthe cavity of the aluminum mold was obtained.

EXAMPLE 82

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyureasilazane and adiepoxide and further comprising a metal filler. A mixture was preparedby handmixing by weight about 50 parts of a diglycidyl ether ofBisphenol "A" (Cat. No. 8760, Dajac Laboratories, Inc., Southhamptom,Pa.) with about 50 parts of Polymer B in an open vessel. A moldingmixture was then prepared by adding about 50 wt %, -325 mesh (particlediameter less than about 45 microns) iron metal powder (Alfa CatalogChemicals, Morton Thiokol, Inc., Danvers, Mass.) to the mixture of theopen vessel and handmixing. The molding mixture comprising the fillerwas then poured into a cavity of an aluminum mold. The molded mixturewas cured by heating at about 120° C. for about 2 hours. A compositionsubstantially replicating the shape of the cavity of the aluminum moldwas obtained.

EXAMPLE 83

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising polybutylmethacrylate and apolyureasilazane. A solution was prepared by dissolving by weight aboutone part of polybutylmethacrylate polymer (ELVACITE® 2045 acrylicbinder, DuPont Company, Wilmington, Del.) in about two parts of xylenesolvent (Cat. No. 24,764-2, Aldrich Chemical Company, Inc., Milwaukee,Wis.). A mixture was then prepared by adding about two parts of thesolution to about one part of Polymer B (to which about 10 wt % oftertbutyl benzoyl peroxide, ATOCHEM North America, Inc., Crosby, Tex.,had been added). The mixture was then allowed to stand to substantiallyevaporate the xylene solvent and produce a molding mixture. About 5grams of the molding mixture were cast into the cavity of an aluminummold. The molded mixture was then heated to about 110° C. for about 2hours. A rigid composition substantially replicating the shape of thecavity of the aluminum mold was obtained.

EXAMPLE 84

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising polybutylmethacrylate and apolyureasilazane polymer and further comprising a glass fiber filler.About 20 grams of a solventless molding mixture made substantiallyaccording to the methods of Example 83 were cast into a cavity of analuminum mold containing four plies of a woven glass fiber mat. The moldmixture embedding the glass fiber mats was heated to about 110° C. forabout 2 hours. A rigid composition comprising glass fiber mats andsubstantially replicating the shape of the cavity of the aluminum moldwas obtained.

EXAMPLE 85

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising polybutylmethacrylate and apolyureasilazane polymer and further comprising metal filler. A moldingmixture was prepared by handmixing about 9 grams of a solventlesscomposition made substantially according to the methods of Example 83and about 4 grams of -325 mesh (particle diameter less than about 45microns) iron metal powder filler (Alfa Catalog Chemicals, MortonThiokol, Inc., Danvers, Mass.). The molding mixture was cast into acavity of an aluminum mold. The molded mixture was heated to about 110°C. for about 2 hours. A rigid composition comprising metal filler andsubstantially replicating the shape of the cavity of the aluminum moldwas obtained.

EXAMPLE 86

The present Example demonstrates, among other things, pour molding acomposition comprising a polysilazane and a polyisocyanate and furthercomprising a ceramic filler. A molding mixture was prepared byhandmixing in an open vessel about 6 grams of Part "A" of a urethanecasting resin (Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.), about 2 grams of 500grit (average particle diameter of about 17 microns) 39 CRYSTOLON® greensilicon carbide powder (Norton Co., Worcester, Mass.) and about 3.5grams of Polymer C. The molding mixture was then poured into a cavity ofan aluminum mold. The molded mixture was cured at about room temperaturein about 2 minutes. A rigid composition comprising ceramic filler andsubstantially replicating the shape of the cavity of the aluminum moldwas obtained.

EXAMPLE 87

The present Example demonstrates, among other things, injection moldinga composition made from a mixture comprising a polysilazane and apolyisocyanate and further comprising a ceramic filler. A mixture wasprepared by handmixing in an open vessel about 14 grams of Part "A" of aurethane casting resin (Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.) and about 5 grams of500 grit (average particle diameter of about 17 microns) 39 CRYSTOLON®green silicon carbide (Norton Co., Worcester, Mass.). A molding mixturewas prepared by handmixing about 6.0 grams of Polymer A to the mixture.The molding mixture was poured into a barrel of an about 10 ml syringeand injected into a cavity of an aluminum mold. The injection moldedmixture cured for about 10 minutes at about room temperature. Acomposition comprising ceramic filler and substantially replicating theshape of the cavity of the aluminum mold was obtained.

EXAMPLE 88

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a diepoxide and apolysilazane. A molding mixture was prepared at about room temperatureby handmixing in an open vessel about 5 grams of a diglycidyl ether ofBisphenol "A" (Cat. No. 8760, Dajac Laboratories, Inc., Southhamptom,Pa.), about 5 grams of Polymer A and about 0.125 grams of phthalic acid(Cat. No. 40,291-5, Aldrich Chemical Company, Inc., Milwaukee, Wis.).The molding mixture was poured into a cavity of an aluminum mold. Themolded mixture was heated to about 150° C. for about 12 hours. A rigid,solid composition substantially replicating the shape of the cavity ofthe aluminum mold was obtained.

EXAMPLE 89

The present Example demonstrates, among other things, reaction injectionmolding (RIM) a composition made from a mixture comprising apolyisocyanate and a polysilazane and further comprising ceramic fillerand carbon fiber filler. A first mixture was prepared by handmixing inan open vessel about 16 grams of Part "A" of a urethane casting resin(Smooth-On™ C-1508 Rigid Urethane Casting Resin; Smooth-On, Inc., 1000Valley Road, Gillette, N.J.) and about 2 grams of 500 grit, 39CRYSTOLON® green silicon carbide (Norton Co., Worcester, Mass.). Thefirst mixture was charged into a first barrel of a syringe ("A" side). Asecond mixture was prepared by handmixing in an open vessel about 6grams of Polymer A and about 2 grams of the 500 grit (average particlediameter of about 17 micron), 39 CRYSTOLON® green silicon carbide(Norton Co., Worcester, Mass.). The second mixture was charged to asecond barrel of the syringe ("B" side). The first and second mixtureswere then simultaneously injected through a mixing zone to induceimpingement mixing to form a molding mixture and into a cavity of analuminum mold containing two stacked plies of woven carbon fiber mat.The molded mixture comprising filler was cured at about room temperaturefor about 15 minutes. A rigid composition comprising fiber andparticulate filler and substantially replicating the shape of the cavityof the mold was obtained.

EXAMPLE 90

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyisocyanate and apolysilazane and further comprising metal filler and carbon fiberfiller. A molding mixture was prepared by handmixing in an open vesselabout 16 grams of Part "A" of a urethane casting resin (Smooth-On™C-1508 Rigid Urethane Casting Resin; Smooth-On, Inc., 1000 Valley Road,Gillette, N.J.), about 5 grams of -325 mesh (particle diameter less thanabout 45 microns) iron metal powder (Alfa Catalog Chemicals, MortonThiokol, Inc., Danvers, Mass.) and about 6 grams of Polymer A. Themolding mixture was then poured into a cavity of an aluminum moldcontaining two plies of woven carbon fiber mat. The molded mixturecomprising the fiber and particulate filler was cured for about 15minutes at about room temperature. A composition comprising fiber andparticulate filler and substantially replicating the shape of the cavityof the aluminum mold was obtained.

EXAMPLE 91

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a diepoxide and apolysilazane and further comprising ceramic filler. A molding mixturewas prepared by handmixing in an open vessel about 7 grams of thediglycidyl ether of Bisphenol "A" (Cat. No. 8760, Dajac Laboratories,Inc., Southhamptom, Pa.), about 7 grams of Polymer A, about 0.18 gramsof phthalic acid (Cat. No. 40,291-5, Aldrich Chemical Company, Inc.,Milwaukee, Wis.) and about 4 grams of 500 grit (average particlediameter of about 17 microns), 39 CRYSTOLON® green silicon carbide(Norton Co., Worcester, Mass.). The molding mixture was poured into acavity of an aluminum mold. The molded mixture was heated to about 150°C. in the mold for about 12 hours. A composition comprising ceramicfiller and substantially replicating the shape of the cavity of thealuminum mold was obtained.

EXAMPLE 92

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a diepoxide and apolysilazane and further comprising a metal filler. A molding mixturewas prepared by handmixing at about room temperature in an open vesselabout 5 grams of a diglycidyl ether of Bisphenol "A" (Cat. No. 8760,Dajac Laboratories, Inc., Southhamptom, Pa.), about 5 grams of PolymerA, about 0.125 grams of phthalic acid (Cat. No. 40,291-5, AldrichChemical Company, Inc., Milwaukee, Wis.), and about 2 grams of aluminummetal powder (UN 1396, Grade 7100, lot #F1621, Alcan Powder & Chemicals,Elizabeth, N.J.). The molding mixture was poured into a cavity of analuminum mold. The molded mixture was heated to about 150° C. for about12 hours. A rigid, solid composition comprising metal filler andsubstantially replicating the shape of the cavity of the aluminum moldwas obtained.

EXAMPLE 93

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a diepoxide and apolysilazane and further comprising fiberglass filler. A molding mixturewas prepared by handmixing in an open vessel about 5 grams of adiglycidyl ether of Bisphenol "A" (Cat. No. 8760, Dajac Laboratories,Inc., Southhamptom, Pa.), about 5 grams of Polymer A, and about 0.125grams of phthalic acid (Cat. No. 40,291-5, Aldrich Chemical Company,Inc., Milwaukee, Wis.). Four plies, measuring about 2"×2" (30.8 mm×50.8mm), of a 8-harness satin weave S-2 glass fiber (Owens/Corning,Huntingdon, Pa.) were layed-up in a cavity of an aluminum mold. Themolding mixture was poured into a cavity of the aluminum mold. Themolded mixture comprising the fiber filler was heated to about 150° C.for about 12 hours. A rigid, solid composition comprising the fiberfiller and substantially replicating the shape of the cavity of thealuminum mold was obtained.

EXAMPLE 94

The present Example demonstrates, among other things, resin-impregnationwith a composition made from a mixture comprising a diepoxide and apolysilazane. A mixture comprising about 49.4 wt % of a diglycidyl etherof Bisphenol "A" (Cat. No. 8760, Dajac laboratories, Inc., Southhampton,Pa.), about 49.4% of Polymer A, and about 1.2 wt % of phthalic acid(Cat. No. 40,291-5, Aldrich Chemical Company, Inc., Milwaukee, Wis.) wasprepared by handmixing in an open vessel. Two about 2"×1" (50.8 mm×25.4mm) strips of woven carbon fiber (about 1 gram) were prepregged byimmersing in about 4 grams of the mixture. After about 15 minutes, theimpregnated carbon fiber mats were wound onto a cylindrical mandrel. Themolded mixture comprising the carbon fiber mats was then heated to about150° C. for about 12 hours. A composition comprising wound fiber fillerand substantially replicating the cylinder was obtained upon removalfrom the mandrel.

EXAMPLE 95

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a polyisocyanate and apolysilazane. A molding mixture was prepared by handmixing at about roomtemperature in an open vessel about 7.3 grams of Part "A" of a urethanecasting resin (Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.), about 2 grams ofabout 180 grit (average particle diameter of about 86 microns) boroncarbide (Elektroschmelzwerk, Kempton (ESK), Germany) and about 3 gramsof Polymer F. The molding mixture was poured into a cavity of analuminum mold. The molded mixture cured at room temperature after about3 hours. A rigid, solid composition substantially replicating the shapeof the cavity of the aluminum mold was obtained.

EXAMPLE 96

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a diepoxide and apolysilazane. A molding mixture was prepared by handmixing at about roomtemperature in an open vessel about 5 grams of a diglycidyl ether ofBisphenol "A" (Cat. No. 8760, Dajac laboratories, Inc., Southhamptom,Pa.) and about 5 grams of Polymer F. A first portion of the moldingmixture was poured into a cavity of a rubber mold. The first portion ofthe molded mixture was cured at about room temperature. After about 24hours a firm, but a tacky composition solid resulted. A second portionof the molding mixture was then cast into a cavity of a second rubbermold. The second portion of the molded mixture was heated to about 80°C. for about 6 hours. A rigid, solid composition substantiallyreplicating the shape of the cavity of the rubber mold was obtained fromthe second portion of molded mixture.

EXAMPLE 97

The present Example demonstrates, among other things, injection moldinga composition made from a mixture comprising polybutylmethacrylate and apolysilazane. A molding mixture was prepared by handmixing in an openvessel about 3 grams of a polybutylmethacrylate polymer (ELVACITE® 2045acrylic binder, DuPont Chemicals, Wilmington, Del.) and about 5 grams ofPolymer F. The molding mixture was loaded into a barrel of a plasticsyringe and injected into a cavity of an aluminum mold. The injectedmolded mixture was cured in the mold at about 100° C. for about 3 hours.A solid composition substantially replicating the shape of the cavity ofthe aluminum mold was obtained.

EXAMPLE 98

The present Example demonstrates, among other things, pour molding of acomposition made from a mixture comprising a diepoxide and apolysilazane and further comprising a ceramic filler. A molding mixturewas prepared by handmixing at about room temperature in an open vesselabout 5 grams of the diglycidyl ether of Bisphenol "A" (Cat. No. 8760,Dajac Laboratories, Inc., Southhamptom, Pa.), about 5 grams of Polymer Fand about 4 grams of 500 grit (average particle diameter of about 17microns) 39 CRYSTOLON® green silicon carbide (Norton Co., Worcester,Mass.). The molding mixture was poured into the cavity of an aluminummold. The molded mixture was cured at about 80° C. for about 6 hours. Arigid, solid composition comprising a filler reinforced part whichsubstantially replicating the shape of the cavity of the aluminum moldwas obtained.

EXAMPLE 99

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising a diepoxide and apolysilazane and further comprising a metal filler. A molding mixturewas prepared by handmixing in an open vessel about 5 grams of thediglycidyl ether of Bisphenol "A" (Cat. No. 8760, Dajac Laboratories,Inc., Southhamptom, Pa.), about 5 grams of Polymer F and about 2 gramsof -325 mesh (particle diameter less than about 45 microns) iron metalpowder (Alfa Catalog Chemicals, Morton Thiokol, Inc., Danvers, Mass.).The molding mixture was poured into a cavity of an aluminum mold. Themolded mixture was cured at about 80° C. for about 6 hours. A rigid,solid composition comprising filler and substantially replicating theshape of the cavity of the aluminum mold was obtained.

EXAMPLE 100

The present Example demonstrates, among other things, molding acomposition further comprising fiber filler made from a mixturecomprising a diepoxide and a polysilazane. A molding mixture wasprepared by handmixing in an open vessel about 5 grams of a diglycidylether of Bisphenol "A" (Cat. No. 8760, Dajac Laboratories, Inc.,Southhamptom, Pa.) and about 5 grams of Polymer F. The molding mixturewas then poured onto a strip of 8 harness satin weave woven fabric (S-2Glass, Owens Corning, Huntington, Pa.) measuring about 2"×10" (50.8mm×254 mm) to make a fiber prepreg. The fiber prepreg was wound onto acylindrical mandrel. The molded prepreg was cured at about 80° C. forabout 6 hours. Upon cooling to about room temperature, the cylindricalmandrel was removed. A rigid, cylindrical composition comprising fiberfiller and substantially conforming to the shape of the cylindricalmandrel was obtained.

EXAMPLE 101

The present Example demonstrates, among other things, molding acomposition made from a mixture comprising a polyisocyanate and apolyalazane. A molding mixture was prepared by handmixing at about roomtemperature in an open vessel about 3 grams of Polymer D and about 8.5grams of Part "A" of a urethane casting resin (Smooth-On™ C-1508 RigidUrethane Casting Resin; Smooth-On, Inc., 1000 Valley Road, Gillette,N.J.). The molding mixture was cast into a cavity of an aluminum mold.The molded mixture was allowed to cure at about room temperature forabout 18 hours. A rubbery, solid composition substantially replicatingthe shape of the cavity of the aluminum mold was obtained.

EXAMPLE 102

The present Example demonstrates, among other things, molding acomposition made from a mixture comprising an epoxy resin and apolyalazane. A molding mixture was prepared by handmixing in an openvessel about 5 grams of Polymer D and about 10 grams of DER 332 EpoxyResin (The Dow Chemical Co., Midland, Mich.) containing about 0.1 gramsof phthalic acid (Cat. No. 40,291-5, Aldrich Chemical Company, Inc.,Milwaukee, Wis.). The molding mixture was cast into a cavity of analuminum mold. The molded mixture was cured to about 100° C. for about18 hours. A rubbery, solid composition substantially replicating theshape of the cavity of the aluminum mold was obtained.

EXAMPLE 103

The present Example demonstrates, among other things, molding acomposition made from a mixture comprising a polyisocyanate and ametal-crosslinked polysilazane. A magnesium-crosslinkedpoly(methylvinyl)silazane was prepared by handmixing in a vessel about250 ml of an about 1 molar solution of dibutylmagnesium in n-heptane(Cat. No. 34,511-3, Aldrich Chemical Company, Inc., Milwaukee, Wis.)chilled to about 0° C. and about 25 grams of Polymer A which was dilutedwith about 25 ml of dry hexane (dried over 13× molecular sieve, Cat. No.29,325-3, Sigma-Aldrich, Sigma Chemical Co., St. Louis, Mo.). Aftercomplete addition, the mixture was heated to reflux. The mixture wasthen stirred overnight at reflux. After the mixture was cooled to aboutroom temperature, ammonia gas was then bubbled through the mixture. Themixture was stripped of solvent under vacuum, to yield a solid, whitemetal-crosslinked polymer.

A molding mixture was prepared by handmixing in an open vessel about 2grams of the metal-crosslinked polymer and about 6.8 grams of Part "A"of a urethane casting resin (Smooth-On™ C-1508 Rigid Urethane CastingResin; Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.). The moldingmixture was then cast into a cavity of an aluminum mold. The moldedmixture was allowed to cure at about room temperature for about 18hours. A partially cured composition was obtained. The partially curedcomposition further cured at about 110° C. for about 6 hours. A solidcomposition substantially replicating the shape of the cavity of thealuminum mold was obtained.

EXAMPLE 104

The present Example demonstrates, among other things, molding acomposition made from a mixture comprising a diepoxide and ametal-crosslinked polysilazane. A molding mixture was prepared byhandmixing at about room temperature in an open vessel about 2 grams ofa magnesium-crosslinked poly(methylvinyl)silazane prepared substantiallyas described in Example 32 and about 7 grams of DER 332 Epoxy Resin (TheDow Chemical Co, Midland, Mich.) containing about 0.1 grams of phthalicacid (Cat. No. 40,291-5, Aldrich Chemical Company, Inc., Milwaukee,Wis.). The molding mixture was cast into a cavity of an aluminum mold.The molded mixture was cured at about 110° C. for about 18 hours. Aweak, solid composition substantially replicating the shape of thecavity of the aluminum mold was obtained.

EXAMPLE 105

The present Example demonstrates, among other things, molding acomposition made from a mixture comprising a diepoxide and apolyborazine. A molding mixture was prepared by handmixing in an openvessel about 7.5 grams of a diglycidyl ether of Bisphenol "A" (Cat. No.8760, Dajac Laboratories, Inc., Southhamptom, Pa.) and about 2.5 gramsof Polymer E. The molding mixture was poured into a cavity of analuminum mold. The molded mixture was cured at about 160° C. for about12 hours. A solid composition substantially replicating the shape of thecavity of the aluminum mold was obtained.

EXAMPLE 106

The present Example demonstrates, among other things, fiber drawing acomposition made from a mixture comprising polybutylmethacrylate and apolyuresilazane. A solution was prepared by dissolving in an open vesselabout 10 g polybutylmethacrylate polymer (ELVACITE® 2045 acrylic binder,DuPont Chemicals, Wilmington, Del.) in about 50 ml of toluene (Cat. No.17,996-5, Aldrich Chemical Company, Inc., Milwaukee, Wis.). About 10 gof Polymer B were added to the solution. The solvent was removed undervacuum and gentle heating at about 35° C. to form a rubbery, colorless,solid composition. The rubbery, colorless, solid composition was heatedto about 110° C., forming a composition comprising viscous melt fromwhich fine, strong fibers up to about 10 feet (3048 mm) in length werehand drawn.

EXAMPLE 107

The present Example demonstrates, among other things, fiber drawing acomposition made from a mixture comprising polybutylmethacrylate and apolysilazane. A solution was prepared by dissolving about 10 g ofpolybutymethacrylate polymer of (ELVACITE® 2045 acrylic binder, DuPontChemicals, Wilmington, Del.) in about 50 ml of toluene (Cat. No.17,996-5, Aldrich Chemical Company, Inc., Milwaukee, Wis.). About 10 gof Polymer C were added to the solution. The solvent was sparged offunder a flow of dry nitrogen at room temperature resulting in acomposition comprising a viscous syrup. Fibers were hand drawn from thiscomposition comprising the viscous syrup. The drawn fibers were aircured at about room temperature for about 5 minutes yielding a strong,flexible, fibrous composition.

EXAMPLE 108

The present Example demonstrates, among other things, a thick filmcomposition made from a mixture comprising polybutylmethacrylate and apolysilazane. A solution was prepared by dissolving in an open vesselabout 10 g of polybutylmethacrylate polymer (ELVACITE® 2045 acrylicbinder, DuPont Chemicals, Wilmington, Del.) in about 50 ml of toluene(Cat. No. 17,996-5, Aldrich Chemical Company, Inc., Milwaukee, Wis.).About 10 g of Polymer C were added to the solution. The solvent wassparged off under a flow of dry nitrogen at room temperature resultingin a composition comprising a viscous syrup. The composition comprisingthe viscous syrup was cast in a thin sheet onto a glass surface. Thecast composition was allowed to cure in air for about 8 hours. A clear,transparent, continuous, flexible, colorless film composition easilyremovable from the glass surface was obtained. The film composition wasabout 0.15 mm thick and slightly elastic.

EXAMPLE 109

The present Example demonstrates, among other things, pour molding acomposition made from a mixture comprising polyureasilazane andcommercially available polyisocyanates.

A solution was prepared in a closeable vessel by first handmixing andthen rollmixing an isocyanate-terminated polyether and polymericmethylene diphenal diisocyanate. A bottle containing VIBRATHANE® B-601polyurethane (a reaction product of a polyether with toluenediisocyanate (TDI), Uniroyal Chemical Co., Inc., Middlebury, Conn.) wasplaced in a water bath at a temperature of about 50° C. Theisocyanate-terminated polyether was heated by the water bath, thusreducing its viscosity. About 100 grams of the heatedisocyanate-terminated polyether were combined with about 427 grams ofRUBINATE® M polymeric methylene diphenyl diisocyanate (MDI) (ICIPolyurethanes Group, West Deptford, N.J.) in a plastic jar. The contentsof the plastic jar were handstirred and then the plastic jar was closedand placed on a roll mill for about 0.5 hours, thereby forming thesolution.

A mixture was made by combining the solution with about 330 grams of-400, +800 mesh (particle diameter from about 15 microns to about 38microns) silicon carbide (Elektroschmelzwerk, Kempton (ESK), Germany).The mixture contained with a sealable container was milled for about 0.5hours using a rolling mill. The mixture was then degassed by opening thecontainer, placing the container in a pressure vessel (W. M. Schmidt &Son, Inc., Chester, Pa.) and allowing the mixture to be subjected to apressure of about 80 pounds per square inch (psi) (about 552 kilopascals(KPa)) for about 15 minutes.

A molding mixture was then prepared. A container with mixture preparedwas then placed in a ice bath to cool the mixture to about 0° C.Additionally, a separate container in which about 133 grams of Polymer Bwas also placed in the ice bath to cool it to about 0° C. The chilledmixture and the about 133 grams of chilled Polymer B were then combinedby handstirring to prepare a molding mixture.

The molding mixture was then cast into a cavity of a rubber mold. Duringthe casting of the molding mixture, the rubber mold was tilted so thatthe molding mixture flowed along the inner surface of the cavity and didnot entrain any of the ambient atmosphere. A second method for castingthe molding mixture included providing the molding mixture to the bottomof the cavity of a rubber mold to effect filling the cavity of therubber mold from its bottom upward (i.e., bottom pouring), therebypreventing the entrainment of any ambient atmosphere. After the moldingmixture was cast into the cavity of the rubber mold, the molding mixturewas degassed by subjecting the molding mixture to a pressure of about 80psi (552 KPa) for about 2 hours, thereby forming the molding mixture.The degassed molded mixture contained within the cavity of the rubbermold was then placed in a furnace at about 50° C. overnight. A moldedcomposition comprising the ceramic filler and substantially replicatingthe shape of the cavity of the rubber mold was obtained. This moldedcomposition was then placed on a bedding of about 90 grit (averageparticle diameter of about 216 micron) 38 ALUNDUM® alumina (Norton Co.,Worcester, Mass.) spread over a ceramic refractory plate to form acuring setup. The curing setup was placed in a furnace initially atabout 110° C. and held there for about 6 hours. Then the temperature ofthe furnace was increase to about 150° C. and held there for about 2hours. A cured molded composition comprising ceramic filler was therebyobtained.

EXAMPLE 110

The present Example demonstrates, among other things, dip coating analuminum substrate with a composition made from a mixture comprisingpolyureasilazane and polybutylmethacrylate. A coating mixture wasprepared by handmixing in an open vessel about 75 grams of Polymer B,about 1.5 grams of DI-CUP® R dicumyl peroxide (Hercules Inc.,Wilmington, Del.), about 50 grams of polybutylmethacrylate (ELVACITE®2045 acrylic binder, DuPont Chemicals, Wilmington, Del.) and about 325grams of xylene (Cat. No. 24,764-2, Aldrich Chemical Company, Inc.,Milwaukee, Wis.). A large aluminum substrate with the surface preparedby sandblasting was coated with the coating mixture by dipping thesubstrate into the coating mixture allowing excess material to drainfrom the dipped part for about 5 minutes. The coating mixture was curedat about 150° C. for about 12 hours. A clear, colorless coatingcomposition exhibiting hardness and abrasion resistance formed. Thecoating composition also exhibited excellent adhesion to the aluminumsubstrate.

EXAMPLE 111

The present Example demonstrates, among other things, pour coating ontoan aluminum substrate a composition made from a mixture comprisingpolyureasilazane and polybutylmethacrylate. The methods of Example 110were substantially repeated to form a coating mixture. However, insteadof dipping the aluminum substrate into the coating mixture, the liquidcoating mixture was poured over the aluminum substrate. The coatedmixture was cured at about 150° C. for about 12 hours. Again, a clear,colorless coating composition exhibiting hardness and abrasionresistance formed. The coating composition also exhibited excellentadhesion to the aluminum substrate.

EXAMPLE 112

The present Example demonstrates, among other things, dip coating asteel substrate with a composition made from a mixture comprisingpolyureasilazane and polybutylmethacrylate. A coating mixture wasprepared by handmixing in an open vessel about 75 grams of Polymer B,about 1.5 grams of DI-CUP® R dicumyl peroxide (Hercules Inc.,Wilmington, Del.), about 50 grams of polybutylmethacrylate (ELVACITE®2045 acrylic binder, DuPont Chemicals, Wilmington, Del.) and about 100grams of xylene (Cat. No. 24,764-2, Aldrich Chemical Company, Inc.,Milwaukee, Wis.). Ten mild steel pipes measuring about 14 inches (355.6mm) long×about 2.5 inches (63.5 mm) outside diameter x about 1/16 inch(1.59 mm) wall thickness were dip-coated into the coating mixture. Thecoating mixture was then cured to about 110° C. for about 2 hours. Asmooth, clear, colorless coating composition exhibiting hardness andabrasion resistance formed. The coating composition also exhibitedexcellent adhesion to the mild steel substrate.

EXAMPLE 113

The present Example demonstrates, among other things, brush coating amild steel mold with a composition made from a mixture comprisingpolyureasilazane and polybutylmethacrylate and further comprisingceramic filler. A syrup was prepared by combining a solution comprisingby weight about 1 part of polybutylmethacrylate (ELVACITE® 2045 acrylicbinder, DuPont Chemicals, Wilmington, Del.) and about 2 parts of xylene(Cat. No. 24,764-2, Aldrich Chemical Company, Inc., Milwaukee, Wis.). Asolution was then prepared by handmixing about 4 parts of the syrup andabout 1 part of Polymer B containing about 10 wt % of benzoyl-tert-butylperoxide (ATOCHEM North America, Inc., Crosby, Tex.). An intermediatesolution was prepared by mixing about 1 part of the resultant solutionand in addition about 1 part xylene. Then, a coating mixture wasprepared by handmixing in an open vessel about 10 grams of 1000 grit(average particle diameter of about 5 microns) boron carbide (B₄ C)(Elektroschmelzwerk, Kempton (ESK), Germany) and an about 20 gramaliquot of the intermediate solution. This coating mixture wasbrush-coated onto the surface of a AISI Type 1015 mild steel coupon. Thecoating mixture was cured by heating the coupon to about 110° C. forabout 1 hour. A continuous black, matte-finish coating compositionexhibiting hardness and abrasion-resistance formed. The coatingcomposition also exhibited excellent adhesion to the mild steel.

EXAMPLE 114

The present Example demonstrates, among other things, dip coating a mildsteel coupon with a composition made from a mixture comprisingpolyureasilazane and polybutylmethacrylate and further comprising metalfiller. A coating mixture was prepared by handmixing in an open vesselabout 10 grams of about 1000 grit (average particle diameter of about 5microns)boron carbide (B₄ C) (Elektroschmelzwerk, Kempton (ESK),Germany), about 10 grams of aluminum powder flake (UN1369, 7100aluminum, Alcan Powders and Chemicals, Elizabeth, N.J.)and about 40grams aliquot of a peroxide-containing,polyureasilazanepolybutylmethacrylate intermediate solution preparedsubstantially in accordance with the methods of Example 113. An AISIType 1015 mild steel coupon was then dipped into the coating mixture.The coating mixture was cured at about 110° C. for about 1 hour. A"silvery" coating composition with a metallic sheen exhibiting goodadhesion to the mild steel formed.

EXAMPLE 115

The present Example demonstrates, among other things, brush coating astainless steel with a composition made from a mixture comprisingpolyureasilazane and polyisocyanate. A coating mixture was prepared byhandmixing in an open vessel about 10.0 grams of methylenediphenyldiisocyanate-derived polyisocyanate (Part "A" of a urethanecasting resin: Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.) and about 5.0 gramsof Polymer B (to which had been added 0.5 wt % of DI-CUP® R dicumylperoxide, Hercules Inc., Wilmington, Del.). The composition was thenbrush-coated onto the surface of an AISI Type 304 stainless steelcoupon. The coated mixture was cured at about room temperature for about1 hour. A transparent, colorless, and glossy coating composition formed.The coating composition exhibited excellent adhesion to the stainlesssteel coupon.

EXAMPLE 116

The present Example demonstrates, among other things, brush coating analuminum coupon with a composition made from a mixture comprisingpolyureasilazane and polyisocyanate and further comprising ceramicfiller. A coating mixture was prepared by handmixing in an open vesselabout 28.7 grams of an about 30 wt % dispersion of 1000 grit (averageparticle diameter about 5 microns) boron carbide (B₄ C) in methylenediphenyldiisocyanate-derived polyisocyanate (Part "A" of a urethanecasting resin: Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.) and about 6 grams ofPolymer B (to which had been added about 0.5 wt % of DI-CUP® R dicumylperoxide, Hercules Inc., Wilmington, Del.). The coating mixture was thenbrush-coated onto a surface of an aluminum coupon. The coated mixtureset at about room temperature for 1 hour, and then cured at about 110°C. for about 1 hour. A very glossy and ebony-colored coating compositionexhibiting excellent hardness and abrasion resistance formed.Furthermore, the coating composition adhered tenaciously to the aluminumcoupon.

EXAMPLE 117

The present Example demonstrates, among other things, pour coating astainless steel with a composition made from a mixture comprisingpolyureasilazane and polyisocyanate and further comprising ceramicfiller. A coating mixture was prepared by handmixing in an open vesselabout 28.7 grams of an about 30 wt % dispersion of 1000 grit (averageparticle diameter about 5 microns) boron carbide (B₄ C) in methylenediphenyldiisocyanate-derived polyisocyanate (Part "A" of a urethanecasting resin: Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.) and about 6 grams ofPolymer B (to which had been added about 0.5 wt % of DI-CUP® R dicumylperoxide, Hercules Inc., Wilmington, Del.). The coating mixture waspoured onto a surface of an AISI Type 304 stainless mixture. The coatedsteel plate, after about 1 hour at about room temperature, was cured toabout 110° C. for about hour. A glossy, black coating compositionexhibiting excellent adhesion to the stainless steel substrate formed.

EXAMPLE 118

The present Example demonstrates, among other things, brush coating astainless steel with a composition made from a mixture comprisingpolyureasilazane and polyisocyanate further comprising metal filler. Acoating mixture was prepared by handmixing in an open vessel about 10.0grams of methylene diphenyldiisocyanate-derived polyisocyanate (Part "A"of a urethane casting resin: Smooth-On™ C-1508 Rigid Urethane CastingResin; Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.), about 5.0grams of Polymer B (to which had been added 0.5 wt % of DI-CUP® Rdicumyl peroxide, Hercules Inc., Wilmington, Del.) and about 3.0 gramsof aluminum flake powder (UN1396, 7100 aluminum, Alcan Powders andChemicals, Elizabeth, N.J.). The coating mixture was brush-coated onto asurface of an AISI Type 304 stainless steel plate. After about 1 hour atabout room temperature, the coating mixture was cured at about 110° C.for about 1 hour. A "silvery" metallic, glossy, composition coatingexhibiting, high hardness, abrasion resistance, and excellent adhesionto the stainless steel plate formed.

EXAMPLE 119

The present Example demonstrates, among other things, brush coating ablock of aluminum with a composition made from a mixture comprisingpolyureasilazane and diepoxide. A coating mixture was prepared byhandmixing in an open vessel about 20 grams of diglycidyl ether ofBisphenol "A" (Cat. No. 8760, Dajac laboratories, Inc., Southhamptom,Pa.), about 20 grams of Polymer B (to which about 0.5 wt % of DI-CUP® Rdicumyl peroxide, Hercules Inc., Wilmington, Del., had been added),about 10 ml of acetone (histological grade, Fisher Chemical, Fairlawn,N.J.) and about 0.5 grams of phthalic acid (Cat. No. 40,291-5, AldrichChemical Company, Inc., Milwaukee, Wis.). The coating mixture wasbrush-coated onto a surface of an aluminum block. The coated mixture wascured at about 150° C. for about 2 hours. A clear, colorless coatingcomposition exhibiting good abrasion resistance, as well as adhesion tothe aluminum block formed.

EXAMPLE 120

The present Example demonstrates, among other things, brush coating ablock of aluminum with a composition made from a mixture comprisingpolyureasilazane and diepoxide and further comprising metal filler. Acoating mixture was prepared by handmixing in an open vessel about 20grams of diglycidyl ether of Bisphenol "A" (Cat. No. 8760, DajacLaboratories, Inc., Southhamptom, Pa.), about 20 grams of Polymer B (towhich about 0.5 wt % of DI-CUP® R dicumyl peroxide, Hercules Inc.,Wilmington, Del., had been added), about 10 ml of acetone (histologicalgrade, Fisher Chemical, Fairlawn, N.J.), about 0.5 grams of phthallicacid (Cat. No. 40,291-5, Aldrich Chemical Company, Inc., Milwaukee,Wis.) and about 10 grams of aluminum metal powder flake (ALCAN UN1396,7100 aluminum, Alcan Powders and Chemicals, Elizabeth, N.J.). Thecoating mixture was brush-coated onto a surface of a block of aluminum.The coated mixture was cured at about 150° C. for about 2 hours. A"silvery" metallic, glossy coating composition exhibiting abrasionresistance formed. The coating composition also exhibited excellentadhesion to the block of aluminum.

EXAMPLE 121

The present Example demonstrates, among other things, brush coating anstainless steel with a composition made from a mixture comprisingpolyureasilazane and diepoxide and further comprising ceramic filler. Acoating mixture was prepared by handmixing in an open vessel about 20grams of diglycidyl ether of Bisphenol "A" (Cat. No. 8760, DajacLaboratories, Inc., Southhamptom, Pa.), about 20 grams of Polymer B (towhich about 0.5 wt % of DI-CUP® R dicumyl peroxide, Hercules Inc.,Wilmington, Del., had been added), about 10 ml of acetone (histologicalgrade, Fisher Chemical, Fairlawn, N.J.), about 0.5 grams of phthallicacid (Cat. No. 40,291-5, Aldrich Chemical Company, Inc., Milwaukee,Wis.) and about 5 grams of 1000 grit (average particle diameter of about5 microns) 39 CRYSTOLON® green silicon carbide powder (Norton Co.,Worcester, Mass.). The coating mixture was brush coated onto a surfaceof an AISI Type 304 stainless steel plate. The coated mixture was curedat about 150° C. for about 2 hours. A "silvery" metallic coatingcomposition exhibiting excellent gloss and abrasion resistance formed.The coating composition also exhibited excellent adhesion to thestainless steel plate.

EXAMPLE 122

The present Example demonstrates, among other things, brush coating anAISI Type 304 stainless steel with a composition made from a mixturecomprising polysilazane and polyisocyanate. A coating mixture wasprepared at about room temperature by handmixing in an open vessel about2.5 grams of Polymer A (containing about 0.5 wt % DI-CUP® R dicumylperoxide, Hercules Inc., Wilmington, Del.) and about 10.0 grams ofmethylene diphenyldiisocyanate polyisocyanate (Part "A" of a urethanecasting resin: Smooth-On™ C-1508 Rigid Urethane Casting Resin;Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.). The coatingcomposition was brush-coated onto a surface of an AISI Type 304stainless steel plate. The coated mixture cured on the plate afterstanding at about room temperature for about 1 hour. A clear, colorlessand glossy coating composition exhibiting good adherence to thestainless steel plate formed.

EXAMPLE 123

The present Example demonstrates, among other things, brush coating ablock of aluminum with a composition made from a mixture comprisingpolysilazane and diepoxide. A coating mixture was prepared by handmixingin an open vessel about 20 grams of the diglycidyl ether of Bisphenol"A" (Cat. No. 8760, Dajac Laboratories, Inc., Southhamptom, Pa.), about20 grams of Polymer A (to which about 0.5 wt % of DI-CUP® R dicumylperoxide, Hercules Inc., Wilmington, Del., had been added), about 10 mlof acetone (histological grade, Fisher Chemical, Fairlawn, N.J.) andabout 0.5 grams of phthallic acid (Cat. No. 40,291-5, Aldrich ChemicalCompany, Inc., Milwaukee, Wis.). The coating mixture was brush-coatedonto a surface of the block of aluminum. The coated mixture was cured atabout 150° C. for about 2 hours. A clear, colorless and glossy coatingcomposition exhibiting good adherence to the block of aluminum formed.

EXAMPLE 124

The present Example demonstrates, among other things, brush coating agraphite cylinder with a composition made from a mixture comprisingpolysilazane and polybutylmethacrylate. A coating mixture was preparedby handmixing in an open vessel about 20 grams of polybutylmethacrylate(ELVACITE® 2045 acrylic binder, DuPont Chemicals, Wilmington, Del.),about 40 ml of xylene (Cat. No. 24,764-2, Aldrich Chemical Company,Inc., Milwaukee, Wis.) and about 20 grams of Polymer A (to which about0.5 wt % DI-CUP® R dicumyl peroxide, Hercules Inc., Wilmington, Del.,had been added). The coating mixture was brush-coated onto a surface ofa graphite cylinder. The coated mixture was cured at about 150° C. forabout 1 hour. A clear, glossy coating composition exhibiting hardnessand abrasion resistance formed. The coating composition also exhibitedexcellent adhesion to the graphite cylinder.

EXAMPLE 125

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprisingpoly(silazane/alazane) and polyisocyanate. A coating mixture wasprepared at about room temperature by handmixing in an open vessel about1.25 grams of Polymer F and about 5.00 grams of methylenediphenyldiisocyanate polyisocyanate (Part "A" of a urethane castingresin: Smooth-On™ C-1508 Rigid Urethane Casting Resin; Smooth-On, Inc.,1000 Valley Road, Gillette, N.J.). The coating composition wasbrush-coated onto a surface of an AISI Type 1015 mild steel coupon. Thecoated mixture cured after about 1 hour at about room temperature. Ayellow coating composition exhibiting good adhesion to the mild steelcoupon formed.

EXAMPLE 126

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprisingpoly(silazane/alazane) and polyisocyanate and further comprising metalfiller. A coating mixture was prepared by handmixing in an open vesselabout 1.25 grams of Polymer F, about 5.00 grams of methylenediphenyldiisocyanate polyisocyanate (Part "A" of a urethane castingresin: Smooth-On™ C-1508 Rigid Urethane Casting Resin; Smooth-On, Inc.,1000 Valley Road, Gillette, N.J.) and about 3.0 grams of aluminum metalflake (ALCAN UN1396, 7100 aluminum, Alcan Powders and Chemicals,Elizabeth, N.J.). The coating mixture was brush-coated onto a surface ofan AISI Type 1015 mild steel coupon. The coated mixture cured afterabout 1 hour at about room temperature. A "silvery", metallic coatingcomposition exhibiting excellent abrasion resistance and very goodadhesion to the mild steel coupon formed.

EXAMPLE 127

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprising apoly(silazane/alazane) and polyisocyanate and further comprising ceramicfiller. A coating mixture was prepared by handmixing in an open vesselabout 1.25 grams of Polymer F, about 5.00 grams of methylenediphenyldiisocyanate polyisocyanate (Part "A" of a urethane castingresin: Smooth-On™ C-1508 Rigid Urethane Casting Resin; Smooth-On, Inc.,1000 Valley Road, Gillette, N.J.) and about 3.0 grams of 1000 grit(average particle diameter of about 5 microns) boron carbide (B₄ C)(Elektroschmelzwerk, Kempton (ESK), Germany) powder. The coating mixturewas brush-coated onto a surface of an AISI Type 1015 mild steel coupon.The coated mixture cured after about 1 hour at about room temperature. Aglossy, black coating composition exhibiting superior abrasionresistance and excellent adhesion to the mild steel substrate formed.

EXAMPLE 128

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprisingpoly(silazane/alazane) and diepoxide. A coating mixture was prepared byhandmixing in an open vessel equal parts of Polymer F and diglycidylether of Bisphenol "A" (Cat. No. 8760, Dajac Laboratories, Inc.,Southhampton, Pa.) and about 5 grams of acetone (histological grade,Fisher Chemical, Fairlawn, N.J.) to make about 10 grams of acomposition. The coating mixture was brush-coated onto a surface of anAISI Type 1015 mild steel coupon. The coated mixture was cured at about150° C. for about 3 hours. An adherent, yellow coating compositionexhibiting some porosity was formed.

EXAMPLE 129

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprisingpoly(silazane/alazane) and polybutylmethacrylate. A coating mixture wasprepared by handmixing in an open vessel equal parts of Polymer F andpolybutylmethacrylate (ELVACITE® 2045 acrylic binder, DuPont Chemicals,Wilmington, Del.) and about 5 grams of xylene (Cat. No. 24,764-2,Aldrich Chemical Company, Inc., Milwaukee, Wis.) to make about 10 gramsof coating mixture. The coating mixture was brush-coated onto a surfaceof an AISI type 1015 mild steel coupon. The coated coupon was heated toabout 150° C. for about 1 hour. A clear, colorless, glossy coatingcomposition exhibiting good abrasion resistance and excellent adhesionto the mild steel substrate formed.

EXAMPLE 130

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprising polyalazaneand polyisocyanate. A coating mixture was prepared at about roomtemperature by handmixing in an open vessel about 1.25 grams of PolymerD and about 5.00 grams of methylene diphenyldiisocyanate polyisocyanate(Part "A" of a urethane casting resin: Smooth-On™ C-1508 Rigid UrethaneCasting Resin; Smooth-On, Inc., 1000 Valley Road, Gillette, N.J.). Thecoating mixture was brush-coated onto a surface of an AISI Type 1015mild steel coupon. The coated mixture was cured at about 150° C. forabout 1 hour. A hard, yellow coating composition exhibiting goodadherence to the mild steel formed.

EXAMPLE 131

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprisingpolyborazine and polyisocyanate. A coating mixture was prepared at aboutroom temperature by handmixing in an open vessel about 1.25 grams ofPolymer E and about 5.00 grams of methylene diphenyldiisocyanatepolyisocyanate (Part "A" of a urethane casting resin: Smooth-On™ C-1508Rigid Urethane Casting Resin; Smooth-On, Inc., 1000 Valley Road,Gillette, N.J.). The coating mixture was brush-coated onto a surface ofan AISI Type 1015 mild steel coupon. The coated mixture was cured atabout 150° C. for about 1 hour. A yellow coating composition exhibitinggood adherence to the mild steel formed.

EXAMPLE 132

The present Example demonstrates, among other things, brush coating amild steel with a composition made from a mixture comprisingpolyborazine and polybutylmethacrylate. A coating mixture was preparedby handmixing in an open vessel by weight equal parts of Polymer E and asyrup prepared by dissolving about 1 part of polybutylmethacrylatepolymer (ELVACITE® 2045 acrylic binder, DuPont Chemicals, Wilmington,Del.) in about 1 part of xylenes (Cat. No. 24,764-2, Aldrich ChemicalCompany, Inc., Milwaukee, Wis.). The coating mixture was brush-coated toa surface of an AISI Type 1015 mild steel coupon. The coated mixture wascured at about 150° C. for about 1 hour. A yellow coating compositionexhibiting good adherence to the mild steel formed.

EXAMPLES 133-139

The present Examples demonstrate, among other things, spray coatingcompositions made from mixtures comprising metal-nitrogen polymers.Table VIII sets forth for Examples 133-139 the coating mixture formedfrom a coating mixture base and a coating mixture dilutant, the coatedsubstrate and the application method the curing temperature and thecuring time for these Examples 133-139. The following is a descriptionof the methods for preparing the coating mixtures and the substrates.

Two coating mixture bases were prepared to make the coating mixtures forthe present Examples. These coating mixture bases are designated Base Aand Base B.

Preparation of Coating Mixture Base A: The coating mixture Base Acomprised a mixture comprising a polyureasilazane and apolybutylmethacrylate. A solution was prepared by combining in acontainer equal parts by weight polybutylmethacrylate polymer (ELVACITE™2045 acrylic binder, DuPont Co., Wilmington, Del.) and about 1 partxylene. After the container was sealed, it was placed on a rolling millfor about 24 hours to substantially completely dissolved thepolybutylmethylmethacrylate into the SUNNYSIDE XY101 xylene (SunnyCorporation, Wheeling, Ill.) and form the solution.

A coating mixture base was then prepared by combining in a container byweight about 2 parts of the solution with about 1 part of Polymer B (towhich had been added about 3 weight percent of DI-CUP® R dicumylperoxide (Hercules Inc., Wilmington, Del.), and in some instances, theDI-CUP® R dicumyl peroxide (Hercules Inc., Wilmington, Del.) wasdissolved in a small gravity of xylene by roll milling prior toaddition). The container was then sealed and placed on a rolling millfor about 24 hours until dicumyl peroxide had substantially completelydissolved thereby forming the coating mixture Base A. The composition ofthe coating mixture Base A comprised by weight about 44.1 percentxylene, about 22 percent

                                      TABLE VIII                                  __________________________________________________________________________    Coating Composition Made from Mixtures Comprising Metal-Nitrogen              Polymers                                                                           Coating Mixture                                                                        Coating Mixture                                                                        Coated  Application                                                                         Curing                                   Example                                                                            Base (Wt %)                                                                            Diluent (Wt %)                                                                         Substrate                                                                             Method                                                                              Temp                                                                              Curing Time                          __________________________________________________________________________    133  Base A (50%)                                                                           Xylene (50%)                                                                           Aluminum                                                                              Spray 225° C.                                                                    20 minutes                           134  Base A (66.7%)                                                                         Xylene (33.3%)                                                                         ASTM Specifi-                                                                         Spray 100° C.                                                                    45 minutes                                                  cation A615 and                                                               A616, Grade 60                                                                Steel                                                  135  Base A (50%)                                                                           Xylene (50%)                                                                           Floor grade                                                                           Spray 100° C.                                                                    45 minutes                                                  commercial                                                                    marble                                                 136  Base A (66.7%)                                                                         Xylene (33.3%)                                                                         Mild Steel                                                                            Spray 100° C.                                                                    45 minutes                           137  Base A (100%)                                                                          N/A      Wood    Brush 100° C.                                                                    15 minutes                           138  Base A (100%)                                                                          N/A      Electrical                                                                            Dip   100° C.                                                                    10 minutes                                                  Grade Copper                                           139  Base B (66.7%)                                                                         Xylene (33.3%)                                                                         Cast iron                                                                             Spray 100° C.                                                                    60 minutes                           __________________________________________________________________________

polymethacrylate, about 32.9 percent Polymer B and about 1 percentdicumyl peroxide.

Preparation of Coating Mixture Base B: The coating mixture of Base B wasmade from a mixture comprising polyureasilazane, dimethyl adipate andpolymethyacrylate. A solution was prepared by combining in a containerby weight about 4 parts DPE-6 dimethyl adipate (DuPont Chemicals,Wilmington, Del.) and about 1 part polybutylmethacrylate (ELVACITE™ 2045acrylic binder, DuPont Chemicals, Wilmington, Del.). After the containerwas sealed, it was placed on a rolling mill for about 24 hours tosubstantially dissolve the polybutylmethacrylate into the dimethyladipate, thereby forming the solution.

A coating mixture base was then prepared by combining in a container byweight about 3 parts of the liquid solution to about 1 part Polymer B(to which had been added about 3 weight percent of DI-CUP® R dicumylperoxide (Hercules Inc., Wilmington, Del.), and in some instances, theDI-CUP® R dicumyl peroxide (Hercules Inc., Wilmington, Del.) wasdissolved in a small gravity of SUNNYSIDE XY101 xylene (SunnyCorporation, Wheeling, Ill.) by roll milling prior to addition). Afterthe container was sealed, it was placed on a rolling mill for about 24hours until the DI-CUP® R dicumyl peroxide (Hercules Inc., Wilmington,Del.) had substantially completely dissolved in the mixture, therebyforming the coating mixture Base B. Coating mixture Base B comprised byweight about 59.5 percent dimethyl adipate, about 14.9 percentpolybutylmethacrylate, about 24.8 percent Polymer B and about 0.8percent DI-CUP® dicumyl peroxide (Hercules Inc., Wilmington, Del.).

Coating mixture Base A and Base B were applied to the substrates setforth in Table VIII either in their full concentration or by dilutionwith additional xylene to form a coating mixture. The substrates werefirst cleaned with a lint-free cloth and in some instances with alcohol.When additional SUNNYSIDE XY101 xylene (Sunny Corporation, Wheeling,Ill.) was used, the coating mixture base and the SUNNYSIDE XY101 xylene(Sunny Corporation, Wheeling, Ill.) were placed in a container and thenonto a rolling mill for about 4 hours to make a uniform blend. When thecoating mixtures were applied by spray coating, the coating mixtureswere poured into the cup of a commercially available syphon-type spraygun (IWATA, Model No. TUG15, obtained from SMART SHOPPERS, Louisville,Ky.) and applied using clean, dry compressed air to obtain asubstantially uniform spray pattern using a pressure between about 25psi (173.4 kPa) and about 60 psi (413.7 kPa). In some instances, thecoating mixtures were cured by heating to the temperatures as set forthin Table VIII for the corresponding times. After the coatings had cured,it was noted that coating compositions exhibiting good adherence to thevarious substrates were obtained.

EXAMPLES 140-148

The present Examples demonstrate, among other things, the formation ofpigmented molded compositions from mixtures comprising a diisocyanateand a metal-nitrogen polymer and further comprising a silica filler.Table IX summarizes for Examples 140-148 the composition in weightpercent of the materials used to formulate the molding mixtures to formthe pigmented molded compositions. The specific materials used to makethe molding mixtures included RUBINATE® M polymer methylene diphenyldiisocyanate (MDI) (ICI Polyurethanes Group, West Deptford, N.J.),VIBRATHANE® B-601 polyurethane (Uniroyal Chemical Co., Inc., Middlebury,Conn.), Grade D, FJ-70 silica sand (Foundry Services Supply Co.,Baltimore, Md.), Polymer B (CERASET® SN preceramic polymer, LanxideCorporation, Newark, Del.) and pigments. The pigments used to make themolding mixtures are summarized in Table IX and included 1000 grit(average particle diameter of about 5 microns) boron carbide(Elektroschmelzwerk, Kempton (ESK), Germany), No. 558, bright yellow,Engobe/slip stain (Standard Ceramic Supply Co., Pittsburgh, Pa.),UN1369, 7100 aluminum powder flake (Alcan Powders and Chemicals,Elizabeth, N.J.), No. 569, turquoise, Engobe/slip stain (StandardCeramic Supply Co., Pittsburgh, Pa.), No. K-38 cobalt blue glaze stain(Standard Ceramic Supply Co., Pittsburgh, Pa.), No. 556 dark greenEngobe/slip stain (Standard Ceramic Supply Co., Pittsburgh, Pa.), andBEN® DW0132 yellow (CIBA-GEIBY Corp., East Lansing, Mich.). The pigmentmolded compositions of Examples 140-148 were made by substantially thesame procedure. Thus, the method for making the pigmented moldedcomposition of Example 140 is described in detail below. An artisan ofordinary skill in the art possesses the skill and understanding to makethe minor modifications to the procedure of Example 140 to form thepigmented molded compositions of Examples 141-148.

                                      TABLE IX                                    __________________________________________________________________________    Pigmented Molded Compositions Made From Mixtures Comprising Isocyanates       and a Silicon-Nitrogen Polymer                                                Composition                                                                                                                    Molded                            RUBINATE ® M.sup.1                                                                  VIBRATHANE ®.sup.2                                                                  Grade D, FJ-70.sup.3    Composition                  Example                                                                            Polymeric MDI                                                                           B-601 Polyurethane                                                                      Silica Sand                                                                            Polymer B                                                                           Pigment  Color                        __________________________________________________________________________    140  23.4 wt % 5.0 wt %  63.8 wt %                                                                              7.1 wt %                                                                            0.7 wt % B.sub.4 C.sup.4                                                               Black                        141  21.3 wt % 7.1 wt %  63.8 wt %                                                                              7.1 wt %                                                                            0.7 wt % B.sub.4 C.sup.4                                                               Black                        142  22.9 wt % 7.6 wt %  61.1 wt %                                                                              7.6 wt %                                                                            0.8 wt % B.sub.4 C.sup.4                                                               Black                        143  22.0 wt % 7.4 wt %  58.8 wt %                                                                              7.4 wt %                                                                            4.4 wt % Yellow                                                               #558 Yellow.sup.5                     144  22.0 wt % 7.4 wt %  58.8 wt %                                                                              7.4 wt %                                                                            4.4 wt % Silver                                                               Al powder.sup.6                       145  22.0 wt % 7.4 wt %  58.8 wt %                                                                              7.4 wt %                                                                            4.4 wt % Turquoise                                                            #569 Turquoise.sup.7                  146  22.0 wt % 7.4 wt %  58.8 wt %                                                                              7.4 wt %                                                                            4.4 wt % Blue                                                                 K-38 Blue.sup.8                       147  22.0 wt % 7.4 wt %  58.8 wt %                                                                              7.4 wt %                                                                            4.4 wt % Green                                                                #556 Green.sup.9                      148  21.0 wt % 7.1 wt %  56.3 wt %                                                                              7.4 wt %                                                                            8.5 wt % Yellow                                                               DW0132 Yellow                         __________________________________________________________________________     .sup.1 RUBINATE ® M polymeric methylene diphenyl diisocyanate (MDI)       (ICI Polyurethanes Group, West Deptford, NJ)                                  .sup.2 VIBRATHANE ® B601 polyurethane (Uniroyal Chemical Co., Inc.,       Middlebury, CT)                                                               .sup.3 Grade D, FJ70 silica sand (Foundry Services Supply Company,            Baltimore, MD)                                                                .sup.4 1000 grit boron carbide (Elektroschmelzwerk, Kempton (ESK),            Germany)                                                                      .sup.5 No. 558 bright yellow Engobe/slip stain (Standard Ceramic Supply       Co., Pittsburgh, PA)                                                          .sup.6 UN1369, 7100 aluminum powder flake (Alcan Powders and Chemicals,       Elizabeth, NJ)                                                                .sup.7 No. 569 turquoise Engobe/slip stain (Standard Ceramic Supply Co.,      Pittsburgh, PA)                                                               .sup.8 No. K38 cobalt blue glaze stain (Standard Ceramic Supply Co.,          Pittsburgh, PA)                                                               .sup.9 No. 556 dark green Engobe/slip stain (Standard Ceramic Supply Co.,     Pittsburgh, PA)                                                               .sup.10 BEN ® DW0132 yellow (CIBAGEIBY Corp, East Lansing, MI)       

EXAMPLE 140

A liquid solution was prepared by combining in a first about 1000 mlHDPE NALGENE® plastic carboy (Nalge Company, Rochester, N.Y.), about 660grams of RUBINATE® M polymeric methylene diphenyl diisocyanate (ICIPolyurethanes Group, West Deptford, N.J.) and about 140 gramsVIBRATHANE® B-601 polyurethane (Uniroyal Chemical Co., Inc., Middlebury,Conn.). After closing, the first plastic carboy was placed on a rollingmill for about 0.5 hours to homogenize the liquid solution.

A precursor molding mixture was prepared by adding to the liquidsolution in the first plastic carboy about 1600 grams of Grade D, FJ-70silica sand (Foundry Services Supply Co., Baltimore, Md.) and about 20grams 1000 grit (average particle diameter of about 5 microns) boroncarbide (Elektroschmelzwerk, Kempton (ESK), Germany). After againclosing, the first plastic carboy and its contents were placed on arolling mill for about 2.5 hours to substantially completely mix thecomponents of the precursor molding mixture. During this time, about 200grams of Polymer B (Lanxide Corporation, Newark, Del.) and about 200grams Grade D, FJ-70 silica sand (Foundry Services Supply Co.,Baltimore, Md.) were combined in a second about 1000 ml HDPE NALGENE®plastic carboy (Nalge Company, Rochester, N.Y.). After closing, thesecond plastic carboy was placed on a rolling mill until Polymer Bsubstantially wet the sand.

In the meantime, the first plastic carboy and its contents were removedfrom the rolling mill. After opening, the first plastic carboy wasplaced under a vacuum bell jar and the precursor molding mixture wasdegassed by exposing the precursor molding mixture to a vacuum of about30 inches (762 mm) of mercury for about 15 minutes.

A molding mixture was then prepared by combining the degassed precursormolding mixture of the first plastic carboy and the Polymer B sandmixture of the second plastic carboy. The molding mixture was vigorouslyhandmixed. When substantially homogeneously mixed, the molding mixturewas cast into a cavity of an aluminum mold (spray coated with apolyester-based paraffin, Price-Driscoll Corp., Farmingdale, N.Y.) whichhad been machined produced a molded object measuring about 12 inches(304.8 mm) square, about 0.25 inch (6.4 mm) high and consisting ofraised truncated domes with a diameter of about 0.9 inch (23 mm), aheight of about 0.2 inch (5 mm) and a center-to-center spacing of about2.3 inches (60 mm) extending for one 12 inch (304.8 mm) square face ofthe molded object.

After about 4 hours at about room temperature, the mold containing themolded mixture was placed into an oven set at about 135° C. for about 12hours. After the mold and its contents were then removed from the oven,a black pigmented molded object substantially replicating the cavity ofthe mold was recovered.

EXAMPLES 141-148

The pigmented molded compositions of Examples 141-148 were made bysubstantially the procedure of Example 140, except that in Examples142-148 no sand was added to Polymer B and in Examples 145-148 the moldcomprised a plastic mold rather than the aluminum mold. In each ofExamples 141-148, a pigmented molded composition substantiallyreplicating the shape of the cavity of the mold was recovered. Thecolors of the pigmented molded compositions are summarized in Table IX.

We claim:
 1. A coating comprising the reaction product of (1) at leastone organic electrophile comprising at least one organic polymercomprising a multiplicity of organic, electrophilic substituents,wherein said electrophilic substituents comprise at least oneelectrophilic reactive group selected from the group consisting ofepoxides, isocyanates and carbonyl-containing groups, and (2) at leastone metal-containing polymer comprising at least one of (i) a polymerselected from the group consisting of silicon-nitrogen polymers,aluminum-nitrogen polymers, and boron-nitrogen polymers comprising therepeat units (a), (b) and (c), ##STR18## respectively, where R, R', R"and R'"=hydrogen, alkyl, alkenyl, alkynyl or aryl and A=O or S; (ii) atleast one mixture of at least two or more polymers comprising two ormore of the structural units of the form (a), (b), (c), and (d),##STR19## where R, R', and R" are defined as above; (iii) at least onemetal-crosslinked polymer comprising one or more of the stuctural unitsof the form (a), (b), (c), and (d); or (iv) at least one copolymercomprising two or more of the structural units of the form (a), (b),(c), and (d).
 2. A coating comprising the reaction product of (1) atleast one organic electrophile comprising at least one organic polymercomprising a multiplicity of organic, electrophilic substituents,wherein said electrophilic substituents comprise at least oneelectrophilic reactive group selected from the group consisting ofepoxides and carbonyl-containing groups, other than a multifunctionalisocyanate or a multifunctional amide, and (2) at least onemetal-nitrogen polymer comprising the repeat unit ##STR20## where R, R',and R"=hydrogen, alkyl, alkenyl, alkynyl or aryl.
 3. A coatingcomprising the reaction product of (1) at least one metal-containingpolymer comprising the repeat unit ##STR21## where R, R', andR"=hydrogen, alkyl, alkenyl, alkynyl, or aryl, and (2) at least 30percent by weight, based on the weight of the metal-containing polymer,of at least one organic electrophile comprising at least one organicpolymer comprising a multiplicity of organic, electrophilic substituentsselected from the group consisting of multifunctional isocyanates andmultifunctional amides.
 4. The coating of claim 2 or 3, wherein said atleast one metal-containing polymer further comprises at least one repeatunit selected from (a), (b), and (c) ##STR22## where R, R' andR"=hydrogen, alkyl, alkenyl, alkynyl or aryl, and A=O or S.
 5. Thecoating of claim 1, 2 or 3, further comprising at least one filler orreinforcement.
 6. The coating of claim 1, 2 or 3, further comprising atleast one free radical generator.
 7. The coating of claim 1, whereinsaid at least one organic polymer comprising a multiplicity ofelectrophilic substituents comprises at least one electrophilicsubstituent selected from the group consisting of at least one diester,at least one polyester, at least one polyacrylate, at least onepolymethacrylate, at least one diepoxide, at least one multifunctionalepoxide, at least one polyimide, at least one polyamide, at least onediisocyanate, and at least one multi-functional isocyanate.
 8. Thecoating of claim 1, wherein said at least one organic electrophilefurther comprises at least one organic monomer or oligomer comprising amultiplicity of electrophilic substituents wherein said electrophilicsubstituents comprise at least one electrophilic reactive group selectedfrom the group consisting of epoxides, carbonyl-containing groups, andisocyanates.
 9. The coating of claim 2 or 3, wherein said at least oneorganic electrophile further comprises at least one additional organicmonomer, oligomer, or polymer comprising a multiplicity of electrophilicsubstituents wherein said electrophilic substituents comprise at leastone electrophilic reactive group selected from the group consisting ofepoxides, carbonyl-containing groups, and isocyanates.
 10. A coatedarticle comprising at least one coating contacting at least a portion ofa body, said at least one coating comprising the reaction product of (1)at least one organic electrophile comprising at least one organicpolymer comprising a multiplicity of organic, electrophilicsubstituents, wherein said electrophilic substituents comprise at leastone electrophilic reactive group selected from the group consisting ofepoxides, carbonyl-containing groups, and isocyanates, and (2) at leastone metal-containing polymer comprising at least one of (i) a polymerselected from the group consisting of silicon-nitrogen polymers,aluminum-nitrogen polymers, and boron-nitrogen polymers comprising therepeat units (a), (b) and (c), ##STR23## respectively, where R, R', R"and R'"=hydrogen, alkyl, alkenyl, alkynyl or aryl and A=O or S; (ii) atleast one mixture of at least two or more polymers comprising two ormore of the structural units of the form (a), (b), (c), and (d),##STR24## where R, R', and R" are defined as above; (iii) at least onemetal-crosslinked polymer comprising one or more of the structural unitsof the form (a), (b), (c), and (d); or (iv) at least one copolymercomprising two or more of the structural units of the form (a), (b),(c), and (d).
 11. A coated article comprising at least one coatingcontacting at least a portion of a body, said at least one coatingcomprising the reaction product of (1) at least one organic electrophilecomprising at least one organic polymer comprising a multiplicity oforganic, electrophilic substituents, wherein said electrophilicsubstituents comprise at least one electrophilic reactive group selectedfrom the group consisting of epoxides and carbonyl-containing groups,other than a multifunctional isocyanate or a multifunctional amide, and(2) at least one metal-nitrogen polymer comprising the repeat units##STR25## where R, R', and R"=hydrogen, alkyl, alkenyl, alkynyl or aryl.12. A coated article comprising at least one coating contacting at leasta portion of a body, said at least one coating comprising the reactionproduct of (1) at least one metal-containing polymer comprising therepeat units ##STR26## where R, R', and R"=hydrogen, alkyl, alkenyl,alkynyl, or aryl, and (2) at least 30 percent by weight, based on theweight of the metal-containing polymer of at least one organicelectrophile comprising an organic polymer comprising a multiplicity ofelectrophilic substituents selected from the group consisting ofmultifunctional isocyanates and multifunctional amides.
 13. The coatedarticle of claim 11 or 12, wherein said metal-containing polymer furthercomprises at least one repeat unit selected from (a), (b), and (c)##STR27## where R, R' and R"=hydrogen, alkyl, alkenyl, alkynyl or aryl,and A=O or S.
 14. The coated article of claim 11 or 12, wherein said atleast one metal-containing polymer comprises at least onemetal-crosslinked polymer.
 15. The coated article of claim 10, 11 or 12,wherein said at least one coating comprises an uncrosslinked reactionproduct.
 16. The coated article of claim 10, 11 or 12, wherein said atleast one coating comprises a crosslinked reaction product.
 17. Thecoated article of claim 10, 11 or 12, wherein said at least one coatingfurther comprises at least one filler or reinforcement.
 18. The coatedarticle of claim 17, wherein said at least one filler or reinforcementcomprises at least one form selected from particulates, whiskers,platelets, chopped fibers, continuous fibers, woven fibers, and fiberlaminates.
 19. The coated article of claim 10, 11 or 12, wherein said atleast one coating further comprises at least one free radical generator.20. The coated article of claim 19, wherein said at least one freeradical generator is selected from peroxides and azo compounds.
 21. Thecoated article of claim 10, wherein said at least one organic polymercomprising a multiplicity of electrophilic substituents comprises atleast one electrophilic substituent selected from the group consistingof at least one diester, at least one polyester, at least onepolyacrylate, at least one polymethacrylate, at least one diepoxide, atleast one multi-functional epoxide, at least one polyimide, at least onepolyamide, at least one diisocyanate, and at least one multi-functionalisocyanate.
 22. The coated article of claim 10, wherein said at leastone organic electrophile further comprises at least one organic monomeror oligomer comprising a multiplicity of electrophilic substituentswherein said electrophilic substituents comprise at least oneelectrophilic reactive group selected from the group consisting ofepoxides, carbonyl-containing groups, and isocyanates.
 23. The coatedarticle of claim 10, wherein said at least one organic electrophilefurther comprises at least one organic monomer or oligomer comprising atleast two electrophilic substituents selected from the group consistingof at least one ester, at least one acrylate, at least one methacrylate,at least one epoxide, at least one isocyanate, at least one imide, andat least one amide.
 24. The coated article of claim 10, wherein said atleast one organic electrophile further comprises at least one organicmonomer or oligomer comprising at least one electrophilic substituentselected from the group consisting of at least one diester, at least onediepoxide, at least one multi-functional epoxide, at least onediisocyanate, and at least one multi-functional isocyanate.
 25. Thecoated article of claim 11 or 12, wherein said at least one organicelectrophile further comprises at least one additional organic monomer,oligomer or polymer comprising a multiplicity of electrophilicsubstituents wherein said electrophilic substituents comprise at leastone electrophilic reactive group selected from the group consisting ofepoxides, carbonyl-containing groups, and isocyanates.
 26. The coatedarticle of claim 11 or 12, wherein said at least one organicelectrophile further comprises at least one additional organic monomer,oligomer or polymer comprising at least two electrophilic substitutentsselected from the group consisting of at least one ester, at least oneacrylate, at least one methacrylate, at least one epoxide, at least oneisocyanate, at least one imide, and at least one amide.
 27. The coatedarticle of claim 11 or 12, wherein said at least one organicelectrophile further comprises at least one additional organic monomer,oligomer or polymer comprising at least one electrophilic substituentselected from the group consisting of at least one diester, at least onediepoxide, at least one multi-functional epoxide, at least onediisocyanate, and at least one multi-functional isocyanate.
 28. Thecoated article of claim 10, 11 or 12, wherein said body comprises atleast one material selected from polymers, ceramics, metals andcombinations thereof.